CN117317265B - Catalyst, preparation method thereof and zinc-air battery - Google Patents
Catalyst, preparation method thereof and zinc-air battery Download PDFInfo
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- CN117317265B CN117317265B CN202311620671.3A CN202311620671A CN117317265B CN 117317265 B CN117317265 B CN 117317265B CN 202311620671 A CN202311620671 A CN 202311620671A CN 117317265 B CN117317265 B CN 117317265B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 67
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 55
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 53
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910052742 iron Inorganic materials 0.000 claims abstract description 36
- 239000013110 organic ligand Substances 0.000 claims abstract description 36
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 24
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims abstract description 23
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 21
- 229910001453 nickel ion Inorganic materials 0.000 claims abstract description 21
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 19
- 238000000197 pyrolysis Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 18
- -1 iron ions Chemical class 0.000 claims description 17
- 239000011148 porous material Substances 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 8
- 239000013177 MIL-101 Substances 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 7
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000011282 treatment Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 150000001721 carbon Chemical group 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 claims 1
- 239000002184 metal Substances 0.000 abstract description 15
- 229910052751 metal Inorganic materials 0.000 abstract description 14
- 230000008569 process Effects 0.000 abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 239000000243 solution Substances 0.000 description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 17
- 239000001301 oxygen Substances 0.000 description 17
- 229910052760 oxygen Inorganic materials 0.000 description 17
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 14
- 229910021645 metal ion Inorganic materials 0.000 description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 10
- 238000006722 reduction reaction Methods 0.000 description 10
- 230000009467 reduction Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 125000003277 amino group Chemical group 0.000 description 8
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 8
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 229910001447 ferric ion Inorganic materials 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000007774 positive electrode material Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- WIOZZYWDYUOMAY-UHFFFAOYSA-N 2,5-diaminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=C(N)C=C1C(O)=O WIOZZYWDYUOMAY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- CJTCBBYSPFAVFL-UHFFFAOYSA-N iridium ruthenium Chemical compound [Ru].[Ir] CJTCBBYSPFAVFL-UHFFFAOYSA-N 0.000 description 2
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 239000013384 organic framework Substances 0.000 description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000011808 electrode reactant Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 238000002186 photoelectron spectrum Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000013354 porous framework Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Classifications
-
- 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
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
Abstract
The application provides a catalyst, a preparation method thereof and a zinc-air battery. The preparation method comprises providing organic ligand, iron source and nickel source, and generating metal organic frame material containing iron ion and nickel ion by hydrothermal reaction; and pyrolyzing the metal organic framework material to obtain the catalyst, wherein the catalyst comprises a porous carbon structure body and an iron-nickel alloy positioned in the porous carbon structure body. The method can improve the difunctional performance of the porous carbon structure body, so that the catalyst has excellent difunctional performance, and the reaction kinetics process is obviously improved.
Description
Technical Field
The application belongs to the technical field of functional composite materials, and particularly relates to a catalyst, a preparation method thereof and a zinc-air battery.
Background
The problem of energy shortage is increasingly serious, and the improvement of the energy storage performance of the battery can effectively relieve the current energy pressure. In the field of chargeable and dischargeable batteries, lithium ion batteries, metal-air batteries, MAB, and the like are generally included, and the lithium ion batteries have relatively low energy density due to the limitation of the highest energy density by electrode materials; the positive electrode of the metal-air battery is oxygen in the atmosphere, the negative electrode reactant is active metal, and high energy can be generated through the reduction of the oxygen in the positive electrode and the oxidation of the negative electrode metal, and the theoretical energy density of the metal-air battery is far higher than that of a lithium ion battery, for example, the energy density of a zinc-air battery ZAB is as high as 1084 Wh.kg -1 。
The zinc-air battery ZAB is usually provided with a positive electrode material added to the positive electrode to regulate and control the performance of the battery through the dual-function kinetic process of oxygen reduction reaction and oxygen evolution reaction. At present, ruthenium oxide and iridium oxide show good difunctional performance, but ruthenium iridium is expensive, has rare reserves and severely limits the large-scale application of the ruthenium iridium.
Therefore, developing a positive electrode material with low cost, high performance and high stability has important practical significance for improving ZAB energy density and wide application.
Disclosure of Invention
The catalyst, the preparation method thereof and the zinc-air battery can improve the difunctional performance of the porous carbon structure body, so that the catalyst has excellent difunctional performance, and the reaction kinetics process is obviously improved.
In a first aspect, the present application provides a method for preparing a catalyst, comprising:
providing an organic ligand, an iron source and a nickel source into an organic solvent, and generating a metal organic framework material containing iron ions and nickel ions through hydrothermal reaction;
and pyrolyzing the metal organic framework material to obtain the catalyst, wherein the catalyst comprises a porous carbon structure body and an iron-nickel alloy positioned in the porous carbon structure body.
In some embodiments, the organic ligand comprises at least one of 2-amino terephthalic acid, 2, 5-diamino terephthalic acid.
In some embodiments, the organic solvent comprises at least one of N, N-dimethylformamide DMF, ethanol.
In some embodiments, the ratio of the amount of material of iron ions in the iron source to the amount of material of nickel ions in the nickel source is 1: (0.3 to 3).
In some embodiments, the total amount of material of iron ions in the iron source and nickel ions in the nickel source is a moles and the amount of material of the organic ligand is B moles, wherein a: b is 1: (0.5 to 1.5).
In some embodiments, the iron source comprises at least one of ferric trichloride, ferric nitrate, ferric sulfate; and/or
In some embodiments, the nickel source comprises at least one of nickel nitrate, nickel acetate, nickel sulfate.
In some embodiments, the temperature of the hydrothermal reaction is 140 ℃ to 160 ℃; and/or the hydrothermal reaction time is 15-20 h.
In some embodiments, the temperature of pyrolysis may be 700 ℃ -900 ℃; and/or pyrolysis time may be 2-4 hours.
In a second aspect, the present application provides a catalyst comprising a porous carbon structure and an iron-nickel alloy located within the porous carbon structure.
In some embodiments, the porous carbon structure comprises a three-dimensional cell structure, and the iron-nickel alloy is located at least within the three-dimensional cell structure.
In some embodiments, the catalyst further comprises a nitrogen atom attached to a carbon atom in the porous carbon structure.
In some embodiments, the ratio of the amount of elemental iron material to the amount of elemental nickel material in the iron-nickel alloy is 1: (0.3 to 3).
In a third aspect, the present application proposes a zinc-air cell comprising an electrode sheet comprising a catalyst prepared according to any of the embodiments of the first aspect of the present application or a catalyst according to any of the embodiments of the second aspect of the present application.
According to the preparation method, the metal organic frame material is prepared by a hydrothermal method, the metal organic frame material is a three-dimensional porous material, and metal ions of the metal organic frame material are iron ions and nickel ions; heat treating the metal organic framework material to cause pyrolysis of the metal organic framework material, wherein organic ligands in the metal organic framework material are pyrolyzed into a porous carbon structure body, and iron ions and nickel ions form an alloy to be loaded in the porous carbon structure body; when the material is applied to a zinc-air battery, the material can provide rich and stable reactive sites while improving the catalytic reaction kinetics, and has excellent charge and discharge performance.
Further, when the organic ligand is a nitrogen-containing organic ligand, the metal organic framework material is functionalized by amino groups, and the metal organic framework material is taken as a precursor to carry out pyrolysis to obtain the catalyst.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments of the present application will be briefly described below, and it is obvious that the drawings described below are only some embodiments of the present application, and that other drawings may be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is an X-ray diffraction XRD pattern of a catalyst according to an embodiment of the present application.
Fig. 2 is a scanning electron microscope SEM photograph of the catalyst in example 1 of the present application.
Fig. 3 is a scanning electron microscope SEM photograph of the catalyst in example 2 of the present application.
Fig. 4 is an XPS spectrum of N1 s X photoelectron spectroscopy of examples 1 and 2 of the present application.
Fig. 5 is a graph of oxygen reduction and oxygen production performance of a zinc-air cell employing a catalyst as the positive electrode material in the examples of the present application.
Fig. 6 is a constant current charge-discharge graph of zinc-air batteries using the catalysts of example 1 and comparative example 1 of the present application as a positive electrode material.
Detailed Description
Hereinafter, embodiments of the catalyst, the method for producing the same, and the zinc-air battery of the present application are specifically disclosed with reference to the accompanying drawings as appropriate. However, unnecessary detailed description may be omitted. For example, detailed descriptions of well-known matters and repeated descriptions of the actual same structure may be omitted. This is to avoid that the following description becomes unnecessarily lengthy, facilitating the understanding of those skilled in the art. Furthermore, the drawings and the following description are provided for a full understanding of the present application by those skilled in the art, and are not intended to limit the subject matter recited in the claims.
Process for preparing catalyst
In a first aspect, the present application provides a method for preparing a catalyst, comprising:
as shown in fig. 1, the preparation method comprises:
step S100, providing an organic ligand, an iron source and a nickel source into an organic solvent, and generating a metal organic framework material containing iron ions and nickel ions through hydrothermal reaction;
step S200, pyrolyzing the metal organic framework material to obtain a catalyst, wherein the catalyst comprises a porous carbon structure body and an iron-nickel alloy positioned in the porous carbon structure body.
According to the preparation method, the metal organic frame material is prepared by a hydrothermal method, the metal organic frame material is a three-dimensional porous material, and metal ions of the metal organic frame material are iron ions and nickel ions; heat treating the metal organic framework material to cause pyrolysis of the metal organic framework material, wherein organic ligands in the metal organic framework material are pyrolyzed into a porous carbon structure body, and iron ions and nickel ions form an alloy to be loaded in the porous carbon structure body; when the material is applied to a zinc-air battery, the material can provide rich and stable reactive sites while improving the catalytic reaction kinetics, and has excellent charge and discharge performance.
Further, when the organic ligand is a nitrogen-containing organic ligand, the metal organic framework material is functionalized by amino groups, and the metal organic framework material is taken as a precursor to carry out pyrolysis to obtain the catalyst.
The specific mechanism of action of the present application is speculated as follows:
the porous carbon structure has the advantages of low cost, strong conductivity, high dual-function performance and the like; iron and nickel serve as transition bimetal, and can be alloyed in the pyrolysis process, so that the dual-function performance of the porous carbon structure body is further improved; and the transition bimetal and the doped nitrogen can form a Metal-N-C site, and the site can effectively improve the oxygen reduction performance, so that the co-modification of the transition bimetal and the doped nitrogen element can further effectively improve the bifunctional performance of the porous carbon structure body, thereby enabling the catalyst to have excellent bifunctional performance and further remarkably improving the reaction kinetics process.
In the related art, transition Metal ions are easy to agglomerate to form alloy particles with larger particle diameters in the pyrolysis process, and the specific porous Metal organic framework material is selected as a carbon source in the embodiment of the application, so that a porous carbon structure with a three-dimensional pore structure is formed, the agglomeration phenomenon in the pyrolysis process can be reduced, the alloy particles are uniformly distributed in the porous carbon structure, metal-N-C active sites on the surface of the material can be increased, the formed catalyst with the porous structure can effectively regulate and control a three-phase reaction interface, the electrochemical active area is increased, and the oxygen reduction performance and the oxygen evolution reaction difunctional kinetic process can be effectively improved.
In addition, the preparation method of the embodiment of the application is simple, good in repeatability, high in natural abundance of raw materials, low in cost and good in application prospect compared with noble metals.
Step S100
The metal organic framework material is a material with a three-dimensional network structure, which is formed by taking metal ions as the center and connecting the metal ions and organic ligands together through strong chemical bonds. The metal organic framework material in the embodiment of the application is mainly MIL-101 material, and the material has relatively large specific surface area, pore volume and pore diameter, and is favorable for forming a multi-pore carbon material in the pyrolysis process.
The preparation method of the metal organic framework material comprises the following specific steps:
step S110, dissolving an organic ligand, an iron source and a nickel source in an organic solvent to obtain a mixed solution;
step S120, adding alkali liquor into the mixed solution, and obtaining suspension through chemical reaction;
and step S130, carrying out hydrothermal reaction on the suspension to generate the metal organic frame material containing iron ions and nickel ions.
In some embodiments, the organic ligands may include nitrogen-containing organic ligands and nitrogen-free organic ligands, and when the organic ligands contain nitrogen atoms, the nitrogen atoms may be introduced in the form of amino groups, the introduction of the amino groups is beneficial to inhibiting coarsening of the bimetallic particles during calcination, and oxygen atoms in the fine particles can consume part of carbon atoms during pyrolysis, thereby helping to construct a porous carbon structure with a three-dimensional pore structure, and in addition, the nitrogen atoms can form Metal-N-C sites with transition bimetallic, so that oxygen reduction performance is improved.
Illustratively, the nitrogen-free organic ligand may include terephthalic acid.
Illustratively, the nitrogen-containing organic ligand may include at least one of 2-amino terephthalic acid, 2, 5-diamino terephthalic acid; the nitrogen-containing organic ligand can be used for amination of the metal organic framework material, so that the metal organic framework material contains a large amount of amino groups, and the metal organic framework material after functionalization of the amino groups can form a nitrogen-doped porous carbon structure body after high-temperature pyrolysis. For example, a nitrogen-containing organic ligand is hydrothermally reacted to produce a metallo-organic framework material containing iron ions and nickel ions, the metallo-organic framework material further comprising nitrogen atoms. And pyrolyzing the metal organic framework material to obtain the catalyst, wherein the catalyst comprises a porous carbon structure containing nitrogen and an iron-nickel alloy positioned in the porous carbon structure, and the nitrogen atoms are connected with carbon atoms in the porous carbon structure.
In some embodiments, the organic solvent comprises at least one of N, N-dimethylformamide DMF, ethanol. The organic solvent molecules can perform weak interaction with the metal organic framework material, and can play a role in further stabilizing the framework structure.
In some embodiments, the iron source may be a ferric iron source, which may include at least one of ferric trichloride, ferric nitrate, ferric sulfate.
In some embodiments, the nickel source may be a divalent nickel source, which may include at least one of nickel nitrate, nickel acetate, nickel sulfate. Ferric ions, divalent nickel ions and nitrogen-containing organic ligands can be converted into the iron-nickel alloy loaded nitrogen-containing porous carbon structure through hydrothermal reaction and pyrolysis treatment.
The ratio of the metal ions to the organic ligands can influence the skeleton performance of the metal organic frame material, the ratio of the amount of the metal ions to the amount of the organic ligands is regulated to be 1 (0.5-1.5), and the skeleton structure of the metal organic frame material can be more stable. Illustratively, the ratio of the amount of total species of metal ions to the amount of species of organic ligand may be 1:0.5, 1:0.8, 1:1.0, 1:1.2, 1:1.5 or a range of any two values recited above.
The metal ions may include ferric ions and divalent nickel ions, and the amount of the substance of the metal ions may be understood as the amount of the total substance of the ferric ions and the divalent nickel ions.
In some embodiments, the ratio of the amount of material of iron ions in the iron source to the amount of material of nickel ions in the nickel source is 1: (0.3-3); specifically, the ratio of the amount of ferric ion species in the iron source to the amount of divalent nickel ion species in the nickel source is 1: (0.3 to 3). When the ratio of the amount of the substance of the ferric ion to the amount of the substance of the divalent nickel ion is in the above range, the metal ions can be substantially coordinated with the organic ligand, and the formed skeleton structure is relatively stable. Illustratively, the ratio of the amount of ferric ion species to the amount of divalent nickel ion species may be 1:0.3, 1:0.5, 1:0.8, 1:1.0, 1:1.2, 1:1.5, 1:1.8, 1:2.0, 1:2.2, 1:2.5, 1:2.6, 1:2.8, 1:3 or a range of any two values mentioned above.
And adding alkali liquor into the mixed solution, and carrying out chemical reaction for about 30-50 min to obtain a suspension, wherein the suspension may be dark brown. In some embodiments, the lye may include at least one of sodium hydroxide, ammonia.
In some embodiments, the concentration of the lye may be 3.5mol/L to 4.5mol/L, for example, 3.5mol/L, 3.6mol/L, 3.7mol/L, 3.8mol/L, 3.9mol/L, 4.0mol/L, 4.1mol/L, 4.2mol/L, 4.3mol/L, 4.4mol/L, 4.5mol/L, or a range of any two of the foregoing values.
In some embodiments, the volume of the lye may be 0.6 mL-0.9 mL, e.g., 0.6mL, 0.7mL, 0.8mL, 0.9mL, or a range of any two of the above values.
In the hydrothermal reaction process, metal ions coordinate with organic ligands to form a metal-organic framework material. The material may be further subjected to washing, drying treatments to provide for subsequent pyrolysis.
In some embodiments, the temperature of the hydrothermal reaction is 140 ℃ to 160 ℃, such as 140 ℃, 142 ℃, 145 ℃, 146 ℃, 148 ℃, 150 ℃, 152 ℃, 155 ℃, 156 ℃, 158 ℃, 160 ℃, or a range of any two of the foregoing values. When the temperature of the hydrothermal reaction is in the range, the metal ions and the organic ligands are fully coordinated, and the stability of the skeleton structure of the metal-organic framework material is improved.
In some embodiments, the hydrothermal reaction time is 15h to 20h, such as 15h, 16h, 17h, 18h, 19h, 20h, or a range of any two values recited above. When the time of the hydrothermal reaction is within the range, the metal ions and the organic ligands are fully coordinated, and the framework structure stability of the metal organic framework material is improved.
Step S200
The metal organic framework material is pyrolyzed and carbonized, the framework structure is a porous carbon structure, and the transition bimetal forming alloy is positioned in the porous framework structure. Further, after the Metal organic framework material is functionalized with an amino group, it contains nitrogen atoms, and during the heat treatment, iron and nickel in the MILs-101 lattice gradually aggregate and alloy to form an iron-nickel alloy with good crystallinity, with which adjacent nitrogen atoms can form a Metal-N structure. Carbon in the MIL-101 structure is gradually carbonized into a carbon matrix, one part of the carbon matrix is wrapped on the surface of the iron-nickel alloy, and the other part of the carbon matrix forms porous carbon with rich pore structures, so that the 3D porous carbon catalyst embedded with the iron-nickel alloy nano particles is formed. It is understood that the catalyst of the present application may be considered to be a nitrogen-rich porous carbon dual function positive electrode electrocatalyst derived from MILs-101 (FeNi).
In some embodiments, the temperature of pyrolysis may be 700 ℃ -900 ℃, such as 700 ℃, 720 ℃, 750 ℃, 760 ℃, 780 ℃, 800 ℃, 820 ℃, 850 ℃, 860 ℃, 870 ℃, 880 ℃, 900 ℃, or a range of any two values above.
In some embodiments, the pyrolysis time may be 2 h-4 h, for example, 2h, 2.2h, 2.5h, 3h, 3.2h, 3.5h, 3.8h, 4h, or a range of any two values.
The temperature is raised from room temperature to 700-900 ℃ at a heating rate of 4-6 ℃/min in an inert atmosphere, and the metal organic frame material is pyrolyzed for 2-4 hours. The inert atmosphere may include at least one of nitrogen and argon.
Catalyst
In a second aspect, the present application provides a catalyst. The catalyst may be prepared by the preparation method of any one of the embodiments of the first aspect of the present application.
The catalyst comprises a porous carbon structure and an iron-nickel alloy positioned in the porous carbon structure. The porous carbon structure has the advantages of strong conductivity, high difunctional performance and the like, and the iron-nickel alloy can improve the difunctional performance of the porous carbon structure, so that the catalyst has excellent difunctional performance, and the reaction kinetics process is obviously improved.
Further, the carbon substrate can form a three-dimensional pore structure, namely the porous carbon structure further comprises a three-dimensional pore structure, and the iron-nickel alloy is at least positioned in the three-dimensional pore structure, so that the effective active area and the conductivity are improved.
When the catalyst further comprises nitrogen atoms, the nitrogen atoms can be connected with carbon atoms in the porous carbon structure body, for example, the nitrogen atoms are connected in a chemical bond mode, and the doping of the nitrogen atoms can assist the formation of a three-dimensional pore channel structure in the porous carbon structure body, so that the iron-nickel alloy is uniformly dispersed in the three-dimensional pore channel structure, the effective active area is improved, and the active sites of the reaction are increased; in addition, nitrogen atoms can form Metal-N-C sites with the iron-nickel alloy, and the sites can effectively improve the oxygen reduction performance, so that the dual-function performance of the porous carbon structure body can be further effectively improved through common modification of transition bimetal and nitrogen element doping, and the catalyst has excellent dual-function performance, so that the reaction kinetics process is remarkably improved.
In some embodiments, the ratio of the amount of elemental iron material to the amount of elemental nickel material in the iron-nickel alloy is 1: (0.3 to 3). When the molar ratio of the iron ions to the nickel ions is in the above range, the bifunctional performance of the catalyst is further improved, and the reaction kinetics process is remarkably improved. Illustratively, the ratio of the amount of elemental iron species to the amount of elemental nickel species may be 1:0.3, 1:0.5, 1:0.8, 1:1.0, 1:1.2, 1:1.5, 1:1.8, 1:2.0, 1:2.2, 1:2.5, 1:2.6, 1:2.8, 1:3 or a range of any two values mentioned above.
Zinc-air battery
In a third aspect, the present application also provides a zinc-air battery.
The zinc-air battery comprises an electrode plate, wherein the electrode plate comprises a catalyst, the catalyst can be used as a catalytic layer material in an anode, and the catalyst can be added to improve the catalytic reaction kinetics and provide rich and stable reactive sites at the same time, so that the zinc-air battery has excellent charge-discharge performance. The catalyst includes a catalyst prepared according to any embodiment of the first aspect of the present application or a catalyst according to any embodiment of the second aspect of the present application.
The zinc-air cell includes a negative electrode, a positive electrode, and an electrolyte, the negative electrode may include zinc metal or zinc alloy. The positive electrode includes a gas diffusion layer, a catalytic layer, and the like, and the catalytic layer includes the catalyst set forth above. The anode has air permeability, so that reactant oxygen in the air can penetrate and diffuse to the zinc metal cathode and undergo oxidation-reduction reaction, and battery charge and discharge are realized.
The technical scheme of the present application will be described below with reference to specific embodiments.
The following embodiments more particularly describe the disclosure of the present application, which are for illustrative purposes only, as various modifications and changes within the scope of the disclosure will be apparent to those skilled in the art. Unless otherwise indicated, all reagents used in the following embodiments are commercially available or are synthetically obtained according to conventional methods and can be used directly without further treatment, as well as the instruments used in the embodiments are commercially available.
Example 1
A method for preparing a catalyst comprising the steps of:
0.724g of 2-aminoterephthalic acid (NH) 2 BDC) in 20mL DMF solution, sonicated for 20 min to bring NH 2 Complete dissolution of BDC to give liquid A.
Weigh 0.540g FeCl 3 •6H 2 O and 0.581g Ni (NO) 3 ) 2 •6H 2 And (3) dissolving the crystal in the solution A completely by ultrasonic treatment for 20 minutes to obtain solution B.
0.4mL of 4mol/L sodium hydroxide aqueous solution was measured and stirred vigorously on a magnetic stirrer for 30 minutes to give a dark brown suspension.
The suspension was transferred to a high temperature high pressure reactor and reacted hydrothermally at 140℃for 18 hours.
The resulting solid was then washed with ethanol by centrifugation for 3 times and dried under vacuum at 80 ℃ for 12 hours to give brown MILs-101 (FeNi) precursor powder.
The brown powder is placed in a tube furnace, heated to 700 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen, and kept for 2 hours, and cooled to room temperature to obtain black powder, namely the catalyst, which is marked as FeNi/N-C-1.
Example 2
A method for preparing a catalyst comprising the steps of:
0.664g of terephthalic acid (BDC) was weighed into 20mL of DMF solution and sonicated for 20 minutes to completely dissolve BDC, resulting in solution A.
Weigh 0.540g FeCl 3 •6H 2 O and 0.581g Ni (NO) 3 ) 2 •6H 2 And (3) dissolving the crystal in the solution A completely by ultrasonic treatment for 20 minutes to obtain solution B.
0.4mL of 4mol/L sodium hydroxide aqueous solution was measured and stirred vigorously on a magnetic stirrer for 30 minutes to give a yellow suspension.
The suspension was transferred to a high temperature high pressure reactor and reacted hydrothermally at 140℃for 18 hours.
The resulting solid was then washed 3 times with ethanol and dried in vacuo at 80℃for 12 hours to give yellow MIL-101 (FeNi) precursor powder.
Then, the yellow powder was placed in a tube furnace, heated to 700 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen, and kept for 2 hours, cooled to room temperature to obtain black powder, namely the catalyst, which was designated as FeNi/C.
Example 3
A method for preparing a catalyst comprising the steps of:
0.724g NH was weighed 2 BDC in 20mL DMF solution, sonicated for 20 minNH is caused to 2 Complete dissolution of BDC to give liquid A.
Weigh 0.810g FeCl 3 •6H 2 O and 0.290g Ni (NO) 3 ) 2 •6H 2 And (3) dissolving the crystal in the solution A completely by ultrasonic treatment for 20 minutes to obtain solution B.
0.4mL of 4mol/L sodium hydroxide aqueous solution was measured and stirred vigorously on a magnetic stirrer for 30 minutes to give a dark brown suspension.
The suspension was transferred to a high temperature high pressure reactor and reacted hydrothermally at 140℃for 18 hours.
The resulting solid was then washed with ethanol by centrifugation for 3 times and dried under vacuum at 80 ℃ for 12 hours to give brown MILs-101 (FeNi) precursor powder.
Then, the brown powder was placed in a tube furnace, heated to 700 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen, and kept at the temperature for 2 hours, and cooled to room temperature to obtain black powder, namely the catalyst, which was designated as FeNi/N-C-2.
Example 4
A method for preparing a catalyst comprising the steps of:
0.724g NH was weighed 2 BDC in 20mL DMF solution, sonicated for 20 min to bring NH 2 Complete dissolution of BDC to give liquid A.
Weigh 0.270g FeCl 3 •6H 2 O and 0.872g Ni (NO) 3 ) 2 •6H 2 And (3) dissolving the crystal in the solution A completely by ultrasonic treatment for 20 minutes to obtain solution B.
0.4mL of 4mol/L sodium hydroxide aqueous solution was measured and stirred vigorously on a magnetic stirrer for 30 minutes to give a dark brown suspension.
The suspension was transferred to a high temperature high pressure reactor and reacted hydrothermally at 140℃for 18 hours.
The resulting solid was then washed with ethanol by centrifugation for 3 times and dried under vacuum at 80 ℃ for 12 hours to give brown MILs-101 (FeNi) precursor powder.
Then, the brown powder was placed in a tube furnace, heated to 700 ℃ at a heating rate of 5 ℃/min under the protection of nitrogen, and kept at the temperature for 2 hours, and cooled to room temperature to obtain black powder, namely the catalyst, which was designated as FeNi/N-C-3.
Comparative example 1
By Pt/C-RuO 2 The catalyst was used as a control material 1.
Performance testing
Half cell performance was tested on a Chenhua electrochemical workstation (CHI 660).
5mg of each of the prepared catalysts was dispersed in 0.5mL of 50% ethanol solution, 50. Mu.L of Nafion solution, a perfluorosulfonic acid type polymer solution, was added, and the mixture was sonicated for 5 hours to obtain a catalyst slurry. 2 mu L of catalyst slurry is taken to be coated on the surface of a disc glassy carbon electrode in a spin mode, and the electrode is dried for 3 minutes under infrared light. A Linear Sweep Voltammetry (LSV) test was performed in 1mol/L potassium hydroxide KOH electrolyte using a graphite rod as a counter electrode and mercury oxide as a reference electrode.
In the single cell performance test, 0.2mL of the catalyst slurry prepared above is uniformly coated on a foam nickel-polytetrafluoroethylene PTFE-carbon paper composite substrate for multiple times, and dried for 5 minutes under infrared light to obtain an air cathode. The prepared air cathode, zinc plate and battery clamp were assembled with 6mol/L KOH (containing 0.2mol/L zinc chloride ZnCl) 2 ) As electrolyte, the test was performed on the blue cell test system CT 3002A.
For comparison experiments, 5mg of 20% Pt/C powder and ruthenium oxide powder were weighed to prepare catalyst slurries for LSV testing and single cell performance testing, respectively.
5mg of the catalyst prepared in the example was combined with Pt/C-RuO 2 The powder was dissolved in 0.5ml of 50% ethanol solution, 25 μl of 5% nafion reagent was added to the above solution, and the solution was sonicated for 2 hours to form a uniform catalyst slurry. The slurry was then applied to a hydrophobic carbon paper-PTFE-nickel foam composite substrate (load of 0.5mg/cm 2 ). Drying under infrared light for 5 minutes to obtain the air electrode. And respectively placing the air anode, the zinc sheet and a 6mol/L potassium hydroxide solution into a self-made zinc-air battery clamp by taking the zinc sheet as a negative electrode, and testing the battery performance by adopting a blue-electricity battery testing system.
Test results
Fig. 1 is an X-ray diffraction XRD pattern of the catalyst in the example of the present application, and in fig. 1, the abscissa 2 Theta defect represents 2 times the incident angle of the X-ray, and the ordinate Intensity represents the peak Intensity.
As shown in fig. 1, the diffraction peaks of example 1 and example 2 correspond well to the standard card of FeNi alloy, thereby illustrating that the catalyst in examples comprises iron-nickel alloy; the mole ratio of iron ions to nickel ions is adjusted, and the mole ratio of iron ions to nickel ions in the iron-nickel alloy has a certain influence on the iron-nickel atomic ratio, so that the iron-nickel atomic ratio is changed. Fig. 2 is a SEM photograph of the catalyst in example 1 of the present application, and fig. 3 is a SEM photograph of the catalyst in example 2 of the present application, wherein the catalyst obtained in example 2 comprises stacked carbon matrix coated nickel-iron alloy nanospheres, and the catalyst obtained in example 1 further comprises 3D porous carbon with rich pore structures embedded with iron-nickel alloy particles, as shown in fig. 2 and 3; it is illustrated that the introduction of amino groups in the organic ligand facilitates the construction of a 3D porous structure that facilitates further improvement of the effective active area and conductivity of the catalyst.
FIG. 4 is an XPS spectrum of N1 s X photoelectron spectrum of example 1 and example 2 of the present application, wherein in FIG. 4, the abscissa Binding energy refers to Binding energy, and the ordinate represents the Intensity of photoelectrons.
As shown in fig. 4, the catalyst prepared in example 1 using 2-amino terephthalic acid as an organic ligand contains nitrogen elements of different chemical environments, while the catalyst prepared in example 2 using terephthalic acid as a ligand does not contain nitrogen elements.
Fig. 5 is a graph of oxygen reduction and oxygen production performance of a zinc-air cell employing a catalyst as the positive electrode material in the examples of the present application. In fig. 5, the abscissa Potential represents the electrode Potential, and the ordinate J represents the current density.
As can be seen from fig. 5, the catalyst prepared in example 1 exhibited the strongest oxygen reduction performance and oxygen production performance. The oxygen reduction performance of the catalyst can be regulated by regulating the doping amount of nitrogen element and the metal ion addition ratio.
Fig. 6 is a constant current charge-discharge graph of a zinc-air battery using the catalysts of example 1 and comparative example 1 as a positive electrode material, and in fig. 6, the abscissa Time represents Time and the ordinate Voltage represents Voltage.
As shown in FIG. 6, at 5mA/cm 2 The catalyst showed superior commercial Pt/C-RuO when operated under constant current conditions for 132 hours 2 The round trip efficiency of the catalyst.
Although illustrative embodiments have been shown and described, it will be understood by those skilled in the art that the foregoing embodiments are not to be construed as limiting the application and that changes, substitutions and alterations of the embodiments may be made without departing from the spirit, principles and scope of the application.
Claims (7)
1. A method for preparing a catalyst, comprising:
step 100, providing an organic ligand, an iron source and a nickel source into an organic solvent, and generating a metal organic framework material containing iron ions and nickel ions through hydrothermal reaction;
step 200, pyrolyzing the metal organic framework material to obtain a catalyst, wherein the catalyst comprises a porous carbon structure body and an iron-nickel alloy positioned in the porous carbon structure body,
the step 100 includes:
completely dissolving an organic ligand in an organic solvent, wherein the organic ligand is 2-amino terephthalic acid;
completely dissolving an iron source and a nickel source in an organic solvent containing an organic ligand to obtain a mixed solution, wherein the iron source is FeCl 3 •6H 2 O, the nickel source is Ni (NO) 3 ) 2 •6H 2 O；
Adding 4mol/L sodium hydroxide aqueous solution into the mixed solution, and obtaining dark brown suspension through chemical reaction;
carrying out hydrothermal reaction on the dark brown suspension to generate a metal organic framework material MIL-101 containing iron ions and nickel ions;
vacuum drying is carried out on the metal organic framework material MIL-101 to obtain brown MIL-101 precursor powder,
wherein the mass ratio of the organic ligand to the iron source to the nickel source to the sodium hydroxide in the sodium hydroxide aqueous solution is 724:540:581:64;
the step 200 includes:
and carrying out pyrolysis treatment on the brown MIL-101 precursor powder, and cooling to room temperature to obtain the catalyst, wherein the catalyst is black powder.
2. The method according to claim 1, wherein the organic solvent comprises at least one of N, N-dimethylformamide and ethanol.
3. The method according to claim 1, wherein,
the temperature of the hydrothermal reaction is 140-160 ℃; and/or the hydrothermal reaction time is 15-20 h.
4. The method according to claim 1, wherein,
the pyrolysis temperature is 700-900 ℃; and/or the pyrolysis time is 2-4 hours.
5. A catalyst prepared by the preparation method of any one of claims 1 to 4.
6. The catalyst according to claim 5, wherein,
the porous carbon structure body comprises a three-dimensional pore structure, and the iron-nickel alloy is at least positioned in the three-dimensional pore structure;
the catalyst also includes a nitrogen atom that is attached to a carbon atom in the porous carbon structure.
7. A zinc-air battery comprising an electrode sheet comprising the catalyst of claim 5 or 6.
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