CN114614027B - Preparation method of CoFe-S@3D-S-NCNT electrode and quasi-solid zinc-air battery - Google Patents
Preparation method of CoFe-S@3D-S-NCNT electrode and quasi-solid zinc-air battery Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 239000007787 solid Substances 0.000 title claims abstract description 41
- 239000002114 nanocomposite Substances 0.000 claims abstract description 63
- 239000000463 material Substances 0.000 claims abstract description 60
- 229910003321 CoFe Inorganic materials 0.000 claims abstract description 32
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 18
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011701 zinc Substances 0.000 claims abstract description 17
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 17
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- 239000002086 nanomaterial Substances 0.000 claims abstract description 13
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 13
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000002135 nanosheet Substances 0.000 claims abstract description 9
- 150000001868 cobalt Chemical class 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 238000000137 annealing Methods 0.000 claims abstract description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- 229910052786 argon Inorganic materials 0.000 claims description 17
- 229920000877 Melamine resin Polymers 0.000 claims description 16
- 239000003792 electrolyte Substances 0.000 claims description 16
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 8
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 8
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 8
- 238000011144 upstream manufacturing Methods 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 7
- 239000004744 fabric Substances 0.000 claims description 6
- 238000011065 in-situ storage Methods 0.000 claims description 6
- 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 claims description 4
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 3
- 239000011245 gel electrolyte Substances 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 230000032683 aging Effects 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 239000011888 foil Substances 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims 4
- 238000004519 manufacturing process Methods 0.000 claims 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 239000007784 solid electrolyte Substances 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 238000003763 carbonization Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 31
- 239000008367 deionised water Substances 0.000 description 30
- 229910021641 deionized water Inorganic materials 0.000 description 30
- 238000001354 calcination Methods 0.000 description 21
- 239000012621 metal-organic framework Substances 0.000 description 19
- 229910052573 porcelain Inorganic materials 0.000 description 18
- 239000000843 powder Substances 0.000 description 13
- 239000002041 carbon nanotube Substances 0.000 description 9
- 229910021393 carbon nanotube Inorganic materials 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 230000010287 polarization Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 7
- 229960002089 ferrous chloride Drugs 0.000 description 6
- 239000012467 final product Substances 0.000 description 6
- 238000011010 flushing procedure Methods 0.000 description 6
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 6
- WSSMOXHYUFMBLS-UHFFFAOYSA-L iron dichloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Fe+2] WSSMOXHYUFMBLS-UHFFFAOYSA-L 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000013112 stability test Methods 0.000 description 4
- LOUWOZBMDAQCRT-UHFFFAOYSA-N cobalt sulfanylideneiron Chemical compound [S].[Fe].[Co] LOUWOZBMDAQCRT-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000010411 electrocatalyst Substances 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- -1 ammonium ions Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000012921 cobalt-based metal-organic framework Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000005486 sulfidation Methods 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 229910001313 Cobalt-iron alloy Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 239000002194 amorphous carbon material Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design 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
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004073 vulcanization Methods 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
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
- H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
-
- 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
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
-
- 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
- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
- H01M4/8673—Electrically conductive fillers
-
- 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
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- 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
A method for preparing CoFe-S@3D-S-NCNT electrode and quasi-solid zinc-air battery. The invention relates to the technical field of chargeable and dischargeable quasi-solid zinc-air batteries, in particular to a preparation method of an electrode and a quasi-solid zinc-air battery comprising the electrode. Cobalt salt, ferric salt and 2-methylimidazole are used as reaction raw materials, a CoFe-MOF nano sheet is obtained by growing at room temperature, and then the CoFe@3D-NCNT micro-nano material is obtained by CVD annealing and carbonization; then carrying out hydrothermal reaction in sodium sulfide solution to obtain the CoFe-S@3D-S-NCNT micro-nano composite material with a 3D micro-nano hierarchical structure, high catalytic activity and better hydrophobicity. And the prepared CoFe-S@3D-S-NCNT composite material is used as a cathode, and is assembled with a zinc anode and a quasi-solid electrolyte to form the quasi-solid zinc-air battery with a sandwich structure. The battery has ideal charge and discharge performance, an open circuit voltage of up to 1.479V and a discharge peak power density of up to 460mW/cm 2 Has excellent charge and discharge stability, and can be circulated for more than 225 times.
Description
Technical Field
The invention relates to the technical field of preparation of quasi-solid rechargeable zinc-air batteries, in particular to the technical field of preparation of new energy materials on an air cathode side.
Background
The quasi-solid zinc-air battery has the advantages of high energy density, portability, small volume, low cost, safety, environmental protection and the like, and has good application prospect. However, the peak power density of the quasi-solid zinc-air battery is low, the stability is poor, and the realization of practical application is still a great challenge. The air electrode is used as a core component of the quasi-solid zinc-air battery, and has important influence on the energy storage density, the discharge peak power density and the cycle life of the battery. Therefore, the development of cathode electrocatalytic materials and air electrodes with high catalytic activity, high stability and high reaction kinetics has great significance for promoting the practical application of high-performance quasi-solid zinc-air batteries, and can also generate remarkable economic value and social benefit. The current development of wearable electronics has made quasi-solid zinc-air batteries attractive, which requires portability of the battery while maintaining high performance, so the design of the battery requires attention to both its electrochemical performance and structural stability.
Platinum carbon, ruthenium oxide, iridium oxide are by far the most effective electrocatalysts for ORR and OER. However, such noble metal materials are expensive and also have poor immunity to fuel oxidizing molecules. And the prepared integrated electrode material cannot have high dual-functional activity, and the assembled quasi-solid zinc-air battery has insufficient performance. Regardless of the challenges, it is important to develop an electrocatalyst that is efficient and durable. Therefore, the cathode material aims to prepare an economic and efficient bifunctional electrocatalyst, namely, the vulcanized cobalt-iron alloy nano particles are coated on the nitrogen-doped carbon nano tube material, wherein cobalt-iron sulfide plays a role in catalyzing an oxygen precipitation reaction (OER) and a role in catalyzing an ORR reaction by the nitrogen-doped carbon nano tube, and in addition, the morphology structure, the conductivity and the surface component defects of the carbon nano tube structure material can mutually and cooperatively promote the catalytic reaction. The prepared cathode catalyst, the zinc anode and the electrolyte form a quasi-solid zinc-air battery with a sandwich structure. The powder air electrode material with high difunctional activity, high power density and excellent stability prepared by the simple method is not reported to be applied to quasi-solid zinc-air batteries.
Disclosure of Invention
In order to solve the problems, the invention provides a CoFe-S@3D-S-NCNT micro-nano composite material, and a preparation method and application thereof. The material has high difunctional activity, and the quasi-solid zinc-air battery with a sandwich structure assembled with a zinc anode and an electrolyte has excellent peak power density and better cycle stability.
According to one of the technical schemes, the CoFe-S@3D-S-NCNT micro-nano composite material is a 3D micro-nano composite structure material with a CoFe alloy carbon nano tube grown on a three-dimensional carbon substrate in situ. The CoFe-S@3D-S-NCN micro-nano composite material has a 3D micro-nano hierarchical structure and good hydrophobicity, and an air cathode, a zinc anode and a quasi-solid electrolyte which are prepared from the CoFe-S@3D-S-NCNT micro-nano composite material form a quasi-solid zinc-air battery with a sandwich structure, and the quasi-solid zinc-air battery has high peak power density and high cycling stability.
The second technical scheme of the invention is that the preparation method of the CoFe-S@3D-S-NCNT micro-nano composite material comprises the following steps: cobalt salt, ferric salt and 2-methylimidazole are used as reaction raw materials, and after CoFe-MOF nano-sheets are obtained, the CoFe@3D-NCNT micro-nano-materials are obtained through CVD annealing carbonization; then carrying out hydrothermal reaction in sodium sulfide aqueous solution to obtain the CoFe-S@3D-S-NCNT micro-nano composite material with the surface covered with cobalt sulfide and cobalt iron sulfide.
Further, the method specifically comprises the following steps:
(1) Preparation of CoFe-MOF nanosheets: aging in a mixed solution consisting of cobalt salt, ferric salt aqueous solution and 2-methylimidazole aqueous solution, and centrifuging, cleaning and drying to obtain CoFe-MOF;
(2) Preparation of CoFe@3D-NCNT: annealing the CoFe-MOF nano sheet in a hydrogen mixing atmosphere in the presence of melamine to obtain a CoFe@3D-NCNT nano material;
(3) Preparation of CoFe-S@3D-S-NCNT: immersing the CoFe@3D-NCNT nano material in sodium sulfide solution for hydrothermal reaction, and washing and drying to obtain the CoFe-S@3D-S-NCNT.
Further, in the step (1), the cobalt salt may be cobalt nitrate, cobalt chloride, or cobalt acetate, the aqueous solution thereof may have a concentration of 5-20g/L, the iron salt may be ferric chloride, ferric nitrate, or ferric acetate, the aqueous solution thereof may have a concentration of 0.5-2g/L, and the 2-methylimidazole aqueous solution may have a concentration of 20-50g/L; stirring for 2-6h, drying at 60deg.C for 10h.
Further, the step (2) specifically includes: placing the CoFe-MOF nano sheet at the downstream of a furnace tube of a tubular atmosphere furnace, placing melamine at the upstream, calcining in an argon+hydrogen atmosphere, then raising the temperature to 700-900 ℃ within 0.5-2 hours, continuously preserving heat for 1-2 hours, and naturally cooling to obtain CoFe@3D-NCNT;
in the mixed atmosphere of argon and hydrogen, the argon accounts for 85-95%, and the hydrogen accounts for 5-15%. In the preferred scheme, in the mixed atmosphere of argon and hydrogen, the argon is 95 percent and the hydrogen is 5 percent.
The mass ratio of melamine to cobalt salt to ferric salt is 0.05-0.2:5-20:5-20. In a high-temperature atmosphere, ammonium ions in melamine have reducibility with a small amount of hydrogen in the atmosphere, so that metal ions in CoFe-MOF can be reduced into metal alloy, and the metal alloy is catalyzed to grow into carbon nanotubes in the presence of a carbon source.
Further, in the step (3): the concentration of the sodium sulfide solution is 10-20g/L; the hydrothermal reaction temperature is 100-140 ℃, and the hydrothermal reaction time is 6-18h.
The sulfide ions in the sodium sulfide solution can form sulfide with partial metal particles in the three-dimensional carbon skeleton under the hydrothermal environment, and also form sulfide with partial alloy in the carbon nano tube, so that the catalytic performance of the catalyst is obviously improved.
The third technical scheme of the invention is the application of the CoFe-S@3D-S-NCNT micro-nano composite material in the air electrode of the quasi-solid zinc-air battery.
According to the fourth technical scheme, the air electrode of the quasi-solid zinc-air battery is prepared by adding ethanol and naphthol solution into the CoFe-S@3D-S-NCNT micro-nano composite material in a proportion of (800-1000 mu L): (40-100 mu L) and ultrasonic mixing for 40-80 min to obtain catalyst ink, dripping the catalyst ink onto carbon paper or carbon cloth, and drying at 50 ℃ to obtain the quasi-solid zinc-air chargeable battery air electrode.
The fifth technical scheme of the invention is that the quasi-solid zinc-air battery anode material is one of zinc sheets, zinc foils, zinc strips, carbon cloth and carbon paper and the like which are subjected to in-situ electrogalvanizing.
According to the sixth technical scheme, the quasi-solid electrolyte material of the quasi-solid zinc-air battery is one of PVA electrolyte, paNa electrolyte, biological cellulose membrane electrolyte and acrylic acid gel electrolyte.
According to the seventh technical scheme, the quasi-solid zinc-air battery is prepared from carbon paper of CoFe-S@3D-S-NCNT nanocomposite serving as a cathode electrode, a zinc anode electrode and electrolyte gel.
Compared with the prior art, the invention has the beneficial effects that:
the CoFe-S@3D-S-NCNT three-dimensional micro-nano composite material has a composite structure that a carbon nano tube grows in situ on a three-dimensional carbon skeleton, the product appearance is uniform, the microstructure has certain hydrophobicity, cobalt iron sulfide has good OER performance, the ORR performance of the carbon nano tube is excellent, and the composite material combines the advantages of the three materials and has high difunctional activity. Due to the improvement of hydrophobicity, more air can be contacted in the electrolyte, so that the discharge electrode is obviously improved, and the power density of the material is further improved.
The preparation method of the CoFe-S@3D-S-NCNT three-dimensional micro-nano composite material air electrode has the advantages of high repeatability, simple synthesis process, easiness in control and the like. The prepared CoFe-S@3D-S-NCNT micro-nano composite material is used as a cathode, a zinc anode and a quasi-solid zinc-air battery consisting of a quasi-solid electrolyte material, and has high difunctional activity, high power density and high stability; is applied to the air electrode of the chargeable quasi-solid zinc-air battery, and has the power density of 460mWcm 2 Long-term stability of 225 cycles.
Drawings
Fig. 1 is an XRD pattern of the product prepared in example 1, wherein: the abscissa X is the diffraction angle (2θ) and the ordinate Y is the relative diffraction intensity.
FIG. 2 is a TEM image of the product prepared in example 1, the object image in panel a being Co 9 S 8 Co and amorphous carbon material, the object image in the b picture is Co 8 FeS 8 And Co 7 Fe 3 。
FIG. 3 is a morphology map (5 μm) of the CoFe-S@3D-S-NCNT micro-nanocomposite prepared in example 1.
FIG. 4 is a morphology map (2 μm) of the CoFe-S@3D-S-NCNT micro-nanocomposite prepared in example 1.
FIG. 5 is a topography of the CoFe@3D-NCNT material prepared in step (2) of example 1.
FIG. 6 is a graph of hydrophobicity of CoFe-S@3D-S-NCNT micro-nanocomposite prepared in example 1.
FIG. 7 is an ORR performance graph of the CoFe-S@3D-S-NCNT micro-nanocomposite prepared in example 1.
FIG. 8 is a graph of OER performance of CoFe-S@3D-S-NCNT micro-nanocomposite prepared in example 1.
FIG. 9 is a graph of ORR stability test performance of the CoFe-S@3D-S-NCNT micro-nanocomposite prepared in example 1.
Fig. 10 is a graph of the PaNa quasi-solid state electrolyte prepared in example 1.
FIG. 11 is an open circuit voltage plot of a rechargeable zinc-air cell for the preparation of CoFe-S@3D-S-NCN micro-T nanocomposite material in example 1.
FIG. 12 is the discharge polarization curve performance results of a rechargeable zinc-air cell of CoFe-S@3D-S-NCN micro-T nanocomposite prepared in example 1.
FIG. 13 is the cycling performance results of a rechargeable zinc-air cell of the CoFe-S@3D-S-NCNT micro-nanocomposite prepared in example 1.
FIG. 14 is a graph of a rechargeable zinc air cell lit LED lamp for CoFe-S@3D-S-NCNT micro-nanocomposite prepared in example 1.
Detailed Description
Various exemplary embodiments of the invention will now be described in detail, which should not be considered as limiting the invention, but rather as more detailed descriptions of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the invention described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present invention. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
Example 1
(1) Preparation of CoFe-MOF
0.582g of cobalt nitrate (Co (NO) 3 ) 2 ·6H 2 O) with 0.06g of ferrous chloride tetrahydrate (FeCl) 2 ·4H 2 O) was dissolved in 40mL of deionized water, mixed with 40mL of deionized water in which 1.32g of 2-methylimidazole (2-MIM) was dissolved, aged at room temperature for 4 hours, and the purple solution was washed by centrifugation with deionized water and ethanol at 6500 rpm for several times, and dried at 80℃for 12 hours.
(2) Preparation of CoFe@3D-NCNT
Placing the prepared purple powder of the CoFe-MOF on the downstream of a porcelain boat, placing melamine on the upstream of the porcelain boat, placing the porcelain boat into a tube furnace for calcination, wherein the calcination atmosphere is 95% argon+5% hydrogen, the calcination temperature is 800 ℃, the heating time is 176 minutes, the heat preservation time is 1 hour, and naturally cooling the tube furnace to obtain the CoFe@3D-NCNT nano material.
(3) Preparation of CoFe-S@3D-S-NCNT
And (3) ultrasonically dissolving 0.7g of sodium sulfide into 40mL of deionized water, transferring to a reaction kettle, immersing the CoFe@3D-NCNT black powder synthesized in the step (2) into the solution, performing hydrothermal reaction for 10 hours at 120 ℃, cooling to room temperature, centrifugally flushing the deionized water and ethanol for several times at the rotating speed of 6500 r, and drying at 80 ℃ to obtain the final product CoFe-S@3D-S-NCNT nanocomposite.
The XRD test results for this example show that: as shown in fig. 1, the abscissa X is the diffraction angle (2θ), and the ordinate Y is the relative diffraction intensity, and the diffraction peak corresponds to the C peak, co peak, and CoFe alloy peak. The reason why sulfide is not present is that the extent of sulfidation in water is weak, and the detection capability of XRD is limited, which is not found.
The TEM test results for this example show that: as shown in FIG. 2, co was found in TEM 9 S 8 Co, amorphous C material, co 7 Fe 3 And Co 8 FeS 8 Demonstration of successful hydrothermal sulfidation to effect transformation of the alloy into sulfide
Performing field emission scanning electron microscope analysis on the nanocomposite prepared in the embodiment, wherein the obtained electron microscope pictures are shown in figures 3-5; wherein, the figures 3-4 are the morphology diagrams of the prepared CoFe-S@3D-S-NCNT micro-nano composite material at the proportions of 5 μm and 3 μm respectively, and the figure 5 is the morphology diagram of the CoFe@3D-NCNT micro-nano material prepared in the step (2); it can be seen that the micro-nano composite structure of the carbon nano tube grown on the three-dimensional carbon skeleton in situ has uniform morphology and typical hydrophobic structure.
Taking the CoFe-S@3D-S-NCNT micro-nano composite material prepared in the embodiment, fully grinding, and sequentially adding ethanol and naphthol solution with the proportion of (800-1000 mu L): (40-100 mu L) and ultrasonic mixing for 40-80 min to obtain catalyst ink, dripping the catalyst ink onto carbon paper or carbon cloth with the area of 1 square centimeter, and drying at 50 ℃ to obtain the quasi-solid zinc-air chargeable battery air electrode.
The prepared CoFe-S@3D-S-NCNT micro-nano composite material is subjected to a hydrophobicity test, and carbon paper loaded with the CoFe-S@3D-S-NCNT micro-nano composite material is directly tested, as shown in FIG. 6, the hydrophobic angle of the carbon paper is 151 degrees, which proves that the CoFe-S@3D-S-NCNT micro-nano composite material has excellent hydrophobicity, and the material with better hydrophobicity is dominant in discharge electrode polarization because a large amount of oxygen is required for the discharge electrode polarization to enable the reaction to proceed forward.
ORR performance test was performed on the prepared CoFe-S@3D-S-NCNT micro-nano composite material, as shown in FIG. 7, which can be seen to have a higher half-wave potential of 0.855V, approaching 6mA/cm 2 Indicating that it has excellent ORR activity.
OER performance test was performed on the prepared CoFe-S@3D-S-NCNT micro-nano composite material, as shown in FIG. 8, and it can be seen that it was at 10mA/cm 2 Only a small 310mV overpotential is sufficient to demonstrate excellent OER performance.
ORR stability test is carried out on the prepared CoFe-S@3D-S-NCNT micro-nano composite material, as shown in FIG. 9, the current density of the prepared CoFe-S@3D-S-NCNT micro-nano composite material can still be kept at 96% of the initial current after 7200S of stability test, and good stability is proved.
And (3) assembling the solid-state battery, namely, assembling the quasi-solid-state zinc-air battery with a sandwich structure by taking the polished zinc sheet as an anode, taking PaNa (sodium polyacrylate) electrolyte and taking carbon paper loaded with CoFe-S@3D-S-NCNT micro-nano composite material as a cathode.
As shown in fig. 10, the electrolyte was a PaNa electrolyte, and it was seen that the electrolyte was a jelly-like gel-like substance.
The discharge polarization performance of the prepared quasi-solid zinc-air battery of CoFe-S@3D-S-NCNT micro-nano composite material is tested, and the result is shown in FIG. 12, and the open circuit voltage can be stabilized at 1.479V in the test time, and the result shows that the quasi-solid zinc-air battery has a larger open circuit voltage.
The discharge polarization performance of the prepared quasi-solid zinc-air battery of CoFe-S@3D-S-NCNT micro-nano composite material was tested, and the result is shown in FIG. 13, the discharge function was normal, and the maximum power density was 460mW/cm 2 The CoFe-S@3D-S-NCNT micro-nano composite material prepared by the method has higher energy conversion efficiency when being assembled into a quasi-solid zinc-air battery with a sandwich structure。
The quasi-solid zinc-air battery of the prepared CoFe-S@3D-S-NCNT micro-nano composite material is subjected to cycle performance detection and cycle charge and discharge, and the battery performance is still stable until 225 cycles of continuous operation are performed as shown in a graph 13, so that the rechargeable zinc-air battery assembled by the CoFe-S@3D-S-NCNT micro-nano composite material prepared by the method has good battery cycle stability.
As shown in FIG. 14, it can be seen that two quasi-solid zinc-air cells prepared from CoFe-S@3D-S-NCNT micro-nano-composite material consisting of CoFe-S@3D-S-NCNT micro-nano-composite material serving as cathode material, paNa electrolyte and zinc sheet can light an LED (3V) lamp.
Example 2
(1) Preparation of CoFe-MOF
0.582g of cobalt nitrate (Co (NO) 3 ) 2 ·6H 2 O) with 0.06g of ferrous chloride tetrahydrate (FeCl) 2 ·4H 2 O) was dissolved in 40mL of deionized water, mixed with 40mL of deionized water in which 1.32g of 2-methylimidazole (2-MIM) was dissolved, aged at room temperature for 4 hours, and the purple solution was washed by centrifugation with deionized water and ethanol at 6500 rpm for several times, and dried at 80℃for 12 hours.
(2) Preparation of CoFe@3D-NCNT
Placing the prepared purple powder of the CoFe-MOF on the downstream of a porcelain boat, placing melamine on the upstream of the porcelain boat, placing the porcelain boat into a tube furnace for calcination, wherein the calcination atmosphere is 95% argon+5% hydrogen, the calcination temperature is 800 ℃, the heating time is 176 minutes, the heat preservation time is 1 hour, and naturally cooling the tube furnace to obtain the CoFe@3D-NCNT nano material.
(3) Preparation of CoFe-S@3D-S-NCNT
And (3) ultrasonically dissolving 0.7g of sodium sulfide into 40mL of deionized water, transferring to a reaction kettle, immersing the CoFe@3D-NCNT black powder synthesized in the step (2) into the solution, performing hydrothermal reaction for 5 hours at 120 ℃, cooling to room temperature, centrifugally flushing the deionized water and ethanol for several times at the rotating speed of 6500 r, and drying at 80 ℃ to obtain the final product CoFe-S@3D-S-NCNT nanocomposite.
Example 3
(1) Preparation of CoFe-MOF
0.582g of cobalt nitrate (Co (NO) 3 ) 2 ·6H 2 O) with 0.06g of ferrous chloride tetrahydrate (FeCl) 2 ·4H 2 O) was dissolved in 40mL of deionized water, mixed with 40mL of deionized water in which 1.32g of 2-methylimidazole (2-MIM) was dissolved, aged at room temperature for 4 hours, and the purple solution was washed by centrifugation with deionized water and ethanol at 6500 rpm for several times, and dried at 80℃for 12 hours.
(2) Preparation of CoFe@3D-NCNT
Placing the prepared purple powder of the CoFe-MOF on the downstream of a porcelain boat, placing melamine on the upstream of the porcelain boat, placing the porcelain boat into a tube furnace for calcination, wherein the calcination atmosphere is 95% argon+5% hydrogen, the calcination temperature is 800 ℃, the heating time is 176 minutes, the heat preservation time is 1 hour, and naturally cooling the tube furnace to obtain the CoFe@3D-NCNT micro-nano material.
(3) Preparation of CoFe-S@3D-S-NCNT
And (3) ultrasonically dissolving 0.7g of sodium sulfide into 40mL of deionized water, transferring to a reaction kettle, immersing the CoFe@3D-NCNT black powder synthesized in the step (2) into the solution, performing hydrothermal reaction for 15 hours at 120 ℃, cooling to room temperature, centrifugally flushing the deionized water and ethanol for several times at the rotating speed of 6500 r, and drying at 80 ℃ to obtain the final product CoFe-S@3D-S-NCNT micro-nano composite material.
The nanocomposite prepared in examples 2 to 3 was subjected to performance verification, the nanocomposite prepared in example 2 had an ORR half-wave potential of 0.84v, an oer overpotential of 350mV, and the nanocomposite prepared in example 3 had an ORR half-wave potential of 0.83v, an oer overpotential of 330mV, and as a result, it was found that the product prepared at a hydrothermal time of 10 hours had more excellent bifunctional activity.
Example 4
(1) Preparation of CoFe-MOF
0.582g of cobalt nitrate (Co (NO) 3 ) 2 ·6H 2 O) with 0.06g of ferrous chloride tetrahydrate (FeCl) 2 ·4H 2 O) dissolved in 40mL of deionized water, mixed with 40mL of deionized water in which 1.32g of 2-methylimidazole (2-MIM) was dissolved, and aged at room temperature for 4 hoursThe purple solution was washed several times with deionized water and ethanol at 6500 rpm and dried at 80℃for 12 hours.
(2) Preparation of CoFe@3D-NCNT
Placing the prepared purple powder of the CoFe-MOF at the downstream of a porcelain boat, placing melamine at the upstream of the porcelain boat, placing the porcelain boat into a tube furnace for calcination, wherein the calcination atmosphere is 95% argon+5% hydrogen, the calcination temperature is 700 ℃, the heating time is 176 minutes, the heat preservation time is 1 hour, and naturally cooling the tube furnace to obtain the CoFe@3D-NCNT nanomaterial.
(3) Preparation of CoFe-S@3D-S-NCNT
And (3) ultrasonically dissolving 0.7g of sodium sulfide into 40mL of deionized water, transferring to a reaction kettle, immersing the CoFe@3D-NCNT black powder synthesized in the step (2) into the solution, performing hydrothermal reaction for 10 hours at 120 ℃, cooling to room temperature, centrifugally flushing the deionized water and ethanol for several times at the rotating speed of 6500 r, and drying at 80 ℃ to obtain the final product CoFe-S@3D-S-NCNT nanocomposite.
Example 5
(1) Preparation of CoFe-MOF
0.582g of cobalt nitrate (Co (NO) 3 ) 2 ·6H 2 O) with 0.06g of ferrous chloride tetrahydrate (FeCl) 2 ·4H 2 O) was dissolved in 40mL of deionized water, mixed with 40mL of deionized water in which 1.32g of 2-methylimidazole (2-MIM) was dissolved, aged at room temperature for 4 hours, and the purple solution was washed by centrifugation with deionized water and ethanol at 6500 rpm for several times, and dried at 80℃for 12 hours.
(2) Preparation of CoFe@3D-NCNT
Placing the prepared purple powder of the CoFe-MOF at the downstream of a porcelain boat, placing melamine at the upstream of the porcelain boat, placing the porcelain boat into a tube furnace for calcination, wherein the calcination atmosphere is 95% argon+5% hydrogen, the calcination temperature is 900 ℃, the heating time is 176 minutes, the heat preservation time is 1 hour, and naturally cooling the tube furnace to obtain the CoFe@3D-NCNT nanomaterial.
(3) Preparation of CoFe-S@3D-S-NCNT
And (3) ultrasonically dissolving 0.7g of sodium sulfide into 40mL of deionized water, transferring to a reaction kettle, immersing the CoFe@3D-NCNT black powder synthesized in the step (2) into the solution, performing hydrothermal reaction for 10 hours at 120 ℃, cooling to room temperature, centrifugally flushing the deionized water and ethanol for several times at the rotating speed of 6500 r, and drying at 80 ℃ to obtain the final product CoFe-S@3D-S-NCNT nanocomposite.
Example 6
(1) Preparation of CoFe-MOF
0.582g of cobalt nitrate (Co (NO) 3 ) 2 ·6H 2 O) with 0.06g of ferrous chloride tetrahydrate (FeCl) 2 ·4H 2 O) was dissolved in 40mL of deionized water, mixed with 40mL of deionized water in which 1.32g of 2-methylimidazole (2-MIM) was dissolved, aged at room temperature for 4 hours, and the purple solution was washed by centrifugation with deionized water and ethanol at 6500 rpm for several times, and dried at 80℃for 12 hours.
(2) Preparation of CoFe@3D-NCNT
Placing the prepared purple powder of the CoFe-MOF at the downstream of a porcelain boat, placing melamine at the upstream of the porcelain boat, placing the porcelain boat into a tube furnace for calcination, wherein the calcination atmosphere is argon, the calcination temperature is 800 ℃, the heating time is 176 minutes, the heat preservation time is 1 hour, and naturally cooling the tube furnace to obtain the CoFe@3D-NCNT nano material.
(3) Preparation of CoFe-S@3D-S-NCNT
And (3) ultrasonically dissolving 0.7g of sodium sulfide into 40mL of deionized water, transferring to a reaction kettle, immersing the CoFe@3D-NCNT black powder synthesized in the step (2) into the solution, performing hydrothermal reaction for 10 hours at 120 ℃, cooling to room temperature, centrifugally flushing the deionized water and ethanol for several times at the rotating speed of 6500 r, and drying at 80 ℃ to obtain the final product CoFe-S@3D-S-NCNT nanocomposite.
The same experimental verification as in example 1 shows that the material prepared in example 2 has a peak power density of 360 mW/cm when used in the preparation of a rechargeable zinc-air cell electrode 2 The cycle stability is more than 180 weeks; the material prepared in example 3 was used in the preparation of a rechargeable zinc-air cell electrode having a peak power density of 380 mW/cm 2 The cycle stability is more than 150 weeks; the material prepared in example 4 was used in the preparation of a rechargeable zinc-air cell electrode having a peak power density of 240 mW/cm 2 Its cycle stability is 110 weeksMore than once; the material prepared in example 5 was used in the preparation of a rechargeable zinc-air cell electrode having a peak power density of 240 mW/cm 2 The cycle stability is more than 140 weeks; the material prepared in example 6 was used in the preparation of a rechargeable zinc-air cell electrode having a peak power density of 120 mW/cm 2 The materials prepared in examples 2-6 have better power density and better cycle stability when used for preparing the rechargeable zinc-air battery electrode, wherein the cycle stability is more than 100 weeks.
Comparative example 1
The difference from example 1 is that no iron element was introduced in step (1), but only Co-MOF alone.
The prepared material is subjected to catalytic activity test and discharge electrode polarization test, the ORR half-wave potential is 0.82V, the OER over-potential is 390mV, and the peak power density is 375 mW/cm 2 The results show that: the electrochemical performance of the pure Co-MOF is reduced after annealing and vulcanization.
Comparative example 2
The difference from example 1 is that the calcination in step (2) is directly carried out by heating to 800℃without introducing melamine as a carbon source, and then the holding time is 1 hour.
The prepared material is tested for morphology, cycle stability and catalytic activity, and is subjected to discharge electrode polarization test, wherein the ORR half-wave potential is 0.73V, the OER overpotential is 430mV, and the peak power density is 140 mW/cm 2 The cycle stability was 85 weeks, and the results showed: after calcination without introducing melamine as a carbon source, the CoFe-MOF nanosheets cannot grow carbon nanotubes in situ, so that the electrochemical performance is reduced, and the power density of the assembled quasi-solid zinc-air battery is poor.
Comparative example 3
The difference from example 1 is that step (3) is omitted.
The prepared material is subjected to catalytic activity test, cycle stability test and discharge electrode polarization test, wherein the ORR half-wave potential is 0.78V, the OER overpotential is 370mV, and the peak power density is 340 mW/cm 2 The cycle stability was 100 weeks, and the results showed that: non-sulfurized product, reduced dual function activity, and assembled zinc-filled voidThe battery power density is poor.
The result shows that the CoFe-S@3D-S-NCNT nanocomposite prepared by the method has high difunctional catalytic activity, and the material is applied to a quasi-solid zinc-air battery, has excellent power density and better cycle stability, promotes the research of an air electrode of the rechargeable zinc-air battery, and plays a certain promotion role in the development of the air electrode material of the high-performance quasi-solid zinc-air battery.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the particular embodiments disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (10)
- The preparation method of the CoFe-S@3D-S-NCNT micro-nano composite material is characterized by comprising the following steps of:(1) Preparation of CoFe-MOF nanosheets: aging in a mixed solution consisting of cobalt salt, ferric salt aqueous solution and 2-methylimidazole aqueous solution, and centrifuging, cleaning and drying to obtain CoFe-MOF;(2) Preparation of CoFe@3D-NCNT: annealing the CoFe-MOF micro-nano sheet in a mixed atmosphere of argon and hydrogen in the presence of melamine to obtain a CoFe@3D-NCNT micro-nano material;(3) Preparation of CoFe-S@3D-S-NCNT: immersing the CoFe@3D-NCNT micro-nano material in sodium sulfide solution for hydrothermal reaction, and washing and drying to obtain the CoFe-S@3D-S-NCNT.
- 2. The method for preparing a CoFe-s@3d-S-NCNT micro-nanocomposite according to claim 1, wherein in the step (1), the cobalt salt comprises cobalt nitrate, cobalt chloride, or cobalt acetate, and the concentration of the aqueous solution is 5-20g/L; the ferric salt comprises ferric chloride, ferric nitrate or ferric acetate, and the concentration of the aqueous solution is 0.5-2g/L; the concentration of the 2-methylimidazole aqueous solution is 20-50g/L.
- 3. The method for preparing a CoFe-S@3D-S-NCNT micro-nano composite material according to claim 1, wherein the argon gas is 85-95% and the hydrogen gas is 5-15% in a mixed atmosphere of argon gas and hydrogen gas.
- 4. The method for producing a CoFe-s@3d-S-NCNT micro-nanocomposite according to claim 1, wherein the argon gas is 95% and the hydrogen gas is 5% in a mixed atmosphere of argon gas and hydrogen gas.
- 5. The method for preparing the CoFe-S@3D-S-NCNT micro-nano composite material according to claim 1, wherein the mass ratio of melamine to cobalt salt to iron salt is 0.05-0.2:5-20:5-20.
- 6. The method for preparing the CoFe-S@3D-S-NCNT micro-nano composite material according to claim 1, wherein in the step (2), coFe-MOF nano sheets are placed at the downstream of a tube-type atmosphere furnace tube, melamine is placed at the upstream, the melamine is placed in an argon and hydrogen atmosphere, the temperature is increased to 700-900 ℃ within 0.5-2 hours, the heat preservation is continued for 1-2 hours, and the CoFe@3D-NCNT is obtained after natural cooling.
- 7. The method for producing CoFe-s@3d-S-NCNT micro nanocomposite according to claim 1, wherein in the step (3): the concentration of the sodium sulfide solution is 10-20g/L.
- 8. The method for producing CoFe-s@3d-S-NCNT micro nanocomposite according to claim 1, wherein in the step (3): the hydrothermal reaction temperature is 100-140 ℃, and the hydrothermal reaction time is 6-18h.
- 9. The quasi-solid state zinc-air rechargeable battery air electrode prepared by the preparation method of any one of claims 1-8 is characterized in that ethanol and naphthol solution are added into the CoFe-S@3D-S-NCNT micro-nano composite material to obtain catalyst ink through ultrasonic dispersion, the catalyst ink is dripped onto carbon paper or carbon cloth, and the carbon paper or carbon cloth is dried to obtain the quasi-solid state zinc-air rechargeable battery air electrode.
- 10. A quasi-solid zinc-air battery comprising an air electrode prepared from the CoFe-s@3d-S-NCNT micro-nano composite material prepared by the preparation method of any one of claims 1 to 8 as a cathode electrode; any one of zinc sheets, zinc foils, zinc strips, carbon cloth or carbon paper in-situ deposited zinc electrodes is used as an anode electrode; any one of PVA electrolyte, paNa electrolyte, biological cellulose film electrolyte and acrylic acid gel electrolyte is used as gel electrolyte to be assembled to obtain the quasi-solid zinc-air battery.
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