CN116613332B - Perovskite nanofiber catalyst and preparation method and application thereof - Google Patents
Perovskite nanofiber catalyst and preparation method and application thereof Download PDFInfo
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- CN116613332B CN116613332B CN202310870075.4A CN202310870075A CN116613332B CN 116613332 B CN116613332 B CN 116613332B CN 202310870075 A CN202310870075 A CN 202310870075A CN 116613332 B CN116613332 B CN 116613332B
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- perovskite
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- nanofiber catalyst
- praseodymium
- electrostatic spinning
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- 239000003054 catalyst Substances 0.000 title claims abstract description 81
- 239000002121 nanofiber Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 31
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 4
- 239000004917 carbon fiber Substances 0.000 claims abstract description 4
- 239000011572 manganese Substances 0.000 claims description 42
- 239000012298 atmosphere Substances 0.000 claims description 29
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 24
- 229920005594 polymer fiber Polymers 0.000 claims description 20
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 19
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 19
- 239000012528 membrane Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 13
- 229910052748 manganese Inorganic materials 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 11
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 11
- 229910017052 cobalt Inorganic materials 0.000 claims description 11
- 239000010941 cobalt Substances 0.000 claims description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 11
- 229910052746 lanthanum Inorganic materials 0.000 claims description 11
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 11
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 9
- 230000001681 protective effect Effects 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910017569 La2(CO3)3 Inorganic materials 0.000 claims description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 229940044175 cobalt sulfate Drugs 0.000 claims description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 claims description 3
- 229960001633 lanthanum carbonate Drugs 0.000 claims description 3
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 claims description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 3
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 claims description 3
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- XIRHLBQGEYXJKG-UHFFFAOYSA-H praseodymium(3+);tricarbonate Chemical compound [Pr+3].[Pr+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O XIRHLBQGEYXJKG-UHFFFAOYSA-H 0.000 claims description 3
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 claims description 3
- LXXCECZPOWZKLC-UHFFFAOYSA-N praseodymium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O LXXCECZPOWZKLC-UHFFFAOYSA-N 0.000 claims description 3
- LHBNLZDGIPPZLL-UHFFFAOYSA-K praseodymium(iii) chloride Chemical compound Cl[Pr](Cl)Cl LHBNLZDGIPPZLL-UHFFFAOYSA-K 0.000 claims description 3
- HWZAHTVZMSRSJE-UHFFFAOYSA-H praseodymium(iii) sulfate Chemical compound [Pr+3].[Pr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HWZAHTVZMSRSJE-UHFFFAOYSA-H 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000011161 development Methods 0.000 abstract description 5
- 239000002105 nanoparticle Substances 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000003837 high-temperature calcination Methods 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000009987 spinning Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229920000557 Nafion® Polymers 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910002422 La(NO3)3·6H2O Inorganic materials 0.000 description 4
- 229910002828 Pr(NO3)3·6H2O Inorganic materials 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 238000004502 linear sweep voltammetry Methods 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 229920001410 Microfiber Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 230000007704 transition Effects 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
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H01M4/90—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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Catalysts (AREA)
- Inert Electrodes (AREA)
Abstract
The invention belongs to the technical field of manufacturing of battery and electrode catalysts, and particularly discloses a perovskite nanofiber catalyst and a preparation method and application thereof. The invention prepares La through electrostatic spinning and high-temperature calcination treatment 0.9 Pr x Co 0.7 Mn 0.3 O 3 (x=0.1, 0.2) perovskite nanofiber catalyst; the perovskite nanofiber catalyst has a structure of La loaded by a carbon fiber framework 0.9 Pr x Co 0.7 Mn 0.3 O 3 . According to the invention, the catalytic activity of the perovskite nanofiber catalyst is greatly improved by doping Pr element; in addition, the carbon fiber skeleton loaded perovskite nano particles also provide more active sites for electrocatalytic reaction, increase the interface contact area of the catalyst, and have good cycle stability, practicability and long-term development prospect when used for assembling rechargeable zinc-air batteries.
Description
Technical Field
The invention relates to the technical field of zinc-air battery and electrode catalyst manufacturing, in particular to a perovskite nanofiber catalyst and a preparation method and application thereof.
Background
Along with the transition from non-renewable energy sources to clean renewable energy sources, the development of sustainable energy storage and conversion devices is of great importance. The zinc-air battery (ZABs) is used as a green energy storage and conversion device, and has the characteristics of rich negative electrode reserves, high theoretical energy density, simple preparation process and the like, so that the zinc-air battery has a large development space in future energy application. Therefore, the cathode catalyst of the high-efficiency zinc-air battery is developed, and the energy conversion of the battery is improvedEfficiency is particularly critical. LaCoMnO 3 As one of the perovskite oxides widely studied, co and Mn elements have excellent catalytic properties and a flexible spin state, so that they have superior catalytic activity. However, the catalyst still has the problems of single performance and unsatisfactory activity, and limits the practical application development.
Therefore, how to provide a perovskite nanofiber catalyst, a preparation method and application thereof, and to improve the catalytic activity of a cathode catalyst, and to improve the cycle stability and the practicability of a battery when the perovskite nanofiber catalyst is applied to the battery are the problems to be solved in the field.
Disclosure of Invention
In view of the above, the invention provides a perovskite nanofiber catalyst, a preparation method and application thereof, so as to solve the problems of single performance and poor activity of the existing cathode catalyst and the problem of poor cycle stability when the perovskite nanofiber catalyst is applied to a battery.
In order to achieve the above purpose, the invention adopts the following technical scheme:
perovskite nanofiber catalyst which is La loaded on carbon fiber framework 0.9 Pr x Co 0.7 Mn 0.3 O 3 Wherein x is 0.1 or 0.2.
Another object of the present invention is to provide a method for preparing a perovskite nanofiber catalyst, comprising the steps of:
1) Mixing a lanthanum source, a praseodymium source, a cobalt source and a manganese source with an organic solvent to obtain an electrostatic spinning precursor solution;
2) Carrying out electrostatic spinning on the electrostatic spinning precursor solution to obtain a high polymer fiber membrane;
3) And heating the polymer fiber membrane in a protective atmosphere, and then heating the polymer fiber membrane in an air atmosphere to obtain the perovskite nanofiber catalyst.
Preferably, the organic solvent is an N, N-dimethylformamide solution of polyvinylpyrrolidone, and the mass concentration of the organic solvent is 12%.
Preferably, the molar mass ratio of the total amount of the lanthanum source, the praseodymium source, the cobalt source and the manganese source to the organic solvent is 1.5-1.575mmol: 4-8 g.
Preferably, the mixing in the step 1) includes stirring, wherein the stirring time is 10-15 h, and the stirring speed is 250-350 rpm.
Preferably, the lanthanum source comprises one or more of lanthanum nitrate, lanthanum nitrate hexahydrate, lanthanum carbonate, lanthanum chloride and lanthanum acetate; the praseodymium source comprises one or more of praseodymium nitrate, praseodymium nitrate hexahydrate, praseodymium carbonate, praseodymium chloride and praseodymium sulfate; the cobalt source comprises one or more of cobalt nitrate, cobalt nitrate hexahydrate, cobalt chloride and cobalt sulfate; the manganese source comprises one or more of manganese acetate, manganese sulfate and manganese chloride.
Preferably, the voltage of the electrostatic spinning in the step 2) is 15-18 kV, and the distance of the electrostatic spinning is 12-15 cm.
Preferably, in the step 3), the heating temperature is 350-450 ℃ and the heating time is 1.5-2.5 h under the protection atmosphere; the heating temperature is 550-650 ℃ and the heating time is 0.8-1.2 h under the air atmosphere.
Preferably, the protective atmosphere includes a rare gas atmosphere and/or a nitrogen atmosphere.
It is still another object of the present invention to provide a use of the perovskite nanofiber catalyst prepared by the preparation method in zinc-air batteries.
Compared with the prior art, the invention has the following beneficial effects:
1. la prepared by the invention 0.9 Pr x Co 0.7 Mn 0.3 O 3 The perovskite nanofiber catalyst is used for an electro-catalytic Oxygen Evolution Reaction (OER) and an Oxygen Reduction Reaction (ORR), and the catalytic activity of the Pr element doped catalyst is obviously improved compared with that of an undoped catalyst; la is subjected to 0.9 Pr 0.1 Co 0.7 Mn 0.3 O 3 The perovskite nanofiber is used as a cathode catalyst assembled battery of a rechargeable zinc-air battery, and has good cycle stability, practicality and long-term development prospect.
2. The preparation method disclosed by the invention is simple and easy to operate, is easy to realize large-scale production, and is convenient to popularize and apply.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a scanning electron microscope image of the perovskite nanofiber catalyst prepared in example 1;
FIG. 2 is a scanning electron microscope image of the perovskite nanofiber catalyst prepared in example 2;
FIG. 3 is the ORR performance test results of the perovskite nanofiber catalyst prepared in example 1;
FIG. 4 is the ORR performance test results of the perovskite nanofiber catalyst prepared in example 2;
fig. 5 is a graph of oxygen evolution performance test results of perovskite nanofiber catalysts.
Detailed Description
The invention provides a perovskite nanofiber catalyst which is La loaded on a carbon fiber framework 0.9 Pr x Co 0.7 Mn 0.3 O 3 Wherein x is 0.1 or 0.2.
The invention also provides a preparation method of the perovskite nanofiber catalyst, which comprises the following steps:
1) Mixing a lanthanum source, a praseodymium source, a cobalt source and a manganese source with an organic solvent to obtain an electrostatic spinning precursor solution;
2) Carrying out electrostatic spinning on the electrostatic spinning precursor solution to obtain a high polymer fiber membrane;
3) And heating the polymer fiber membrane in a protective atmosphere, and then heating the polymer fiber membrane in an air atmosphere to obtain the perovskite nanofiber catalyst.
In the invention, the organic solvent is N, N-dimethylformamide solution of polyvinylpyrrolidone, and the mass concentration of the organic solvent is 12%.
In the invention, the molar mass ratio of the total amount of the lanthanum source, the praseodymium source, the cobalt source and the manganese source to the organic solvent is 1.5-1.575mmol: 4-8 g, specifically 1.5mmol:5g, 1.5mmol:6g, 1.5mmol:7g, 1.575mmol:5g, 1.575mmol:6g, 1.575mmol:7g.
In the invention, the mole ratio of lanthanum source, praseodymium source, cobalt source and manganese source is 0.9:0.1:0.7:0.3 or 0.9:0.2:0.7:0.3.
in the invention, the mixing in the step 1) comprises stirring, wherein the stirring time is 10-15 h, and specifically can be 11h, 12h, 13h and 14h; the stirring speed is 250-350 rpm, and specifically, 260rpm, 280rpm, 300rpm, 320rpm and 340rpm.
In the invention, the lanthanum source comprises one or more of lanthanum nitrate, lanthanum nitrate hexahydrate, lanthanum carbonate, lanthanum chloride and lanthanum acetate; the praseodymium source comprises one or more of praseodymium nitrate, praseodymium nitrate hexahydrate, praseodymium carbonate, praseodymium chloride and praseodymium sulfate; the cobalt source comprises one or more of cobalt nitrate, cobalt nitrate hexahydrate, cobalt chloride and cobalt sulfate; the manganese source comprises one or more of manganese acetate, manganese sulfate and manganese chloride.
In the invention, the voltage of the electrostatic spinning in the step 2) is 15-18 kV, and can be specifically 16kV or 17kV; the electrostatic spinning distance is 12-15 cm, and the spinning distance can be specifically 12.5cm, 13cm, 13.5cm, 14cm and 14.5cm.
In the invention, the heating temperature in the step 3) under the protective atmosphere is 350-450 ℃, specifically 360 ℃, 380 ℃, 400 ℃, 420 ℃ and 440 ℃; the heating time is 1.5-2.5 h, and can be specifically 1.6h, 1.8h, 2h, 2.2h and 2.4h.
In the invention, the temperature heated in the air atmosphere in the step 3) is 550-650 ℃, specifically 560 ℃, 580 ℃, 600 ℃, 620 ℃ and 640 ℃; the heating time is 0.8-1.2 h, and can be specifically 0.9h, 0.95h, 1h, 1.05h, 1.1h and 1.15h.
In the present invention, the protective atmosphere includes a rare gas atmosphere and/or a nitrogen atmosphere, and the rare gas atmosphere includes a helium atmosphere, a neon atmosphere, and an argon atmosphere.
The invention also provides application of the perovskite nanofiber catalyst prepared by the preparation method in zinc-air batteries.
In the present invention, the perovskite nanofiber catalyst is applied to the cathode of a zinc-air cell.
In the invention, the perovskite nanofiber catalyst is applied as follows:
the perovskite nanofiber catalyst is mixed with carbon black, water, ethanol and Nafion, loaded on carbon paper, and then coated on a diffusion layer to serve as a cathode of the zinc-air battery.
In the invention, the mass volume ratio of the perovskite nanofiber catalyst to carbon black, water, ethanol and Nafion is preferably 4-6 mg: 4-6 mg: 320-360 mu L: 150-170 mu L:18 to 22. Mu.L, more preferably 5mg:5mg:340 μL:160 μL: 20. Mu.L.
In the invention, the mixing comprises ultrasonic mixing, wherein the ultrasonic time is 15-25 min, and can be specifically 16min, 17min, 18min, 19min, 20min, 22min and 24min; the load capacity is 1.8-2.2 mg/cm 2 Specifically, it may be 1.9mg/cm 2 、2mg/cm 2 、2.1mg/cm 2 。
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
0.675 mmol La (NO 3 ) 3 ·6H 2 O、0.075 mmol Pr(NO 3 ) 3 ·6H 2 O、0.225 mmol (CH 3 COO) 2 Mn、0.525 mmol Co(NO 3 ) 2 ·6H 2 O was added to 5g of a 12 wt% PVP (K90)/DMF solution and stirred at 300rpm at room temperature for 12h to give an electrostatic spinning precursor solution (La 0.9 Pr 0.1 Co 0.7 Mn 0.3 O 3 PVP/DMF). Obtaining La after electrostatic spinning 0.9 Pr 0.1 Co 0.7 Mn 0.3 PVP polymer fiber film (electrostatic spinning process: spinning voltage 16kV, spinning distance 14 cm). La is subjected to 0.9 Pr 0.1 Co 0.7 Mn 0.3 The PVP polymer fiber membrane is calcined at 400 ℃ for 2h in a nitrogen atmosphere in a tube furnace, and then heated to 600 ℃ and kept at 1h in an air atmosphere, so as to obtain the perovskite nanofiber catalyst.
The result of scanning electron microscope detection is shown in figure 1, and from figure 1, it can be seen that the prepared perovskite nanofiber catalyst presents nanofiber shape, and simultaneously, a plurality of pore structures are formed on the nanofiber surface, and the carbon fiber skeleton is loaded with La 0.9 Pr 0.1 Co 0.7 Mn 0.3 O 3 Perovskite nano particles provide more active sites for electrocatalytic reaction, and increase the interface contact area of the catalyst.
Example 2
0.675 mmol La (NO 3 ) 3 ·6H 2 O、0.15mmol Pr(NO 3 ) 3 ·6H 2 O、0.225 mmol (CH 3 COO) 2 Mn、0.525 mmol Co(NO 3 ) 2 ·6H 2 O was added to 5g of a 12 wt% PVP (K90)/DMF solution and stirred at 300rpm at room temperature for 12h to give an electrostatic spinning precursor solution (La 0.9 Pr 0.2 Co 0.7 Mn 0.3 O 3 PVP/DMF). Obtaining La after electrostatic spinning 0.9 Pr 0.2 Co 0.7 Mn 0.3 PVP polymer fiber film (electrostatic spinning process: spinning voltage 16kV, spinning distance 14 cm). La is subjected to 0.9 Pr 0.2 Co 0.7 Mn 0.3 The PVP polymer fiber membrane is calcined at 400 ℃ for 2h in a nitrogen atmosphere in a tube furnace, and then heated to 600 ℃ and kept at 1h in an air atmosphere, so as to obtain the perovskite nanofiber catalyst.
The result of scanning electron microscope detection is shown in figure 2, and it can be seen from figure 2 that the prepared perovskite nanofiber catalyst presents nanofiber shape, and simultaneously the nanofiber surface forms a plurality of holesStructure, carbon fiber skeleton load La 0.9 Pr 0.2 Co 0.7 Mn 0.3 O 3 Perovskite nano particles provide more active sites for electrocatalytic reaction, and increase the interface contact area of the catalyst.
Example 3
0.675 mmol La (NO 3 ) 3 ·6H 2 O、0.075mmol Pr(NO 3 ) 3 ·6H 2 O、0.225 mmol (CH 3 COO) 2 Mn、0.525 mmol Co(NO 3 ) 2 ·6H 2 O was added to 4 g of a 12 wt% PVP (K90)/DMF solution and stirred at 350rpm at room temperature for 15h to give an electrostatic spinning precursor solution (La 0.9 Pr 0.1 Co 0.7 Mn 0.3 O 3 PVP/DMF). Obtaining La after electrostatic spinning 0.9 Pr 0.1 Co 0.7 Mn 0.3 PVP polymer fiber film (electrostatic spinning process: spinning voltage 16kV, spinning distance 12 cm). La is subjected to 0.9 Pr 0.1 Co 0.7 Mn 0.3 The PVP polymer fiber membrane is calcined at 380 ℃ for 2.5h in a nitrogen atmosphere in a tube furnace, and then heated to 650 ℃ in an air atmosphere and kept at 0.8 h, so as to obtain the perovskite nanofiber catalyst.
Example 4
0.675 mmol La (NO 3 ) 3 ·6H 2 O、0.15mmol Pr(NO 3 ) 3 ·6H 2 O、0.225 mmol (CH 3 COO) 2 Mn、0.525 mmol Co(NO 3 ) 2 ·6H 2 O was added to 7g of a 12 wt% PVP (K90)/DMF solution and stirred at 260rpm at room temperature for 10 hours to give an electrostatic spinning precursor solution (La 0.9 Pr 0.2 Co 0.7 Mn 0.3 O 3 PVP/DMF). Obtaining La after electrostatic spinning 0.9 Pr 0.2 Co 0.7 Mn 0.3 PVP polymer fiber film (electrostatic spinning process: spinning voltage 18kV, spinning distance 15 cm). La is subjected to 0.9 Pr 0.2 Co 0.7 Mn 0.3 Calcining PVP polymer fiber membrane at 450 deg.C under nitrogen atmosphere in tubular furnace for 2.5. 2.5h, heating to 550 deg.C under air atmosphere and maintaining at 1h to obtain perovskite nanometerA rice fiber catalyst.
Experimental example 1
Electrochemical performance test:
the Oxygen Evolution Reaction (OER) activity was determined using a conventional three electrode system with Hg/HgO (sat. KOH) electrode as reference electrode and graphite rod as counter electrode. The marchst CS350H electrochemical workstation was used for testing. First, a four-necked flask containing 1M KOH was filled with oxygen (99.9%) for half an hour, followed by 50 cycles of CV activation. Then recorded by Linear Sweep Voltammetry (LSV) at a scan rate of 5 mV/s. The stability test uses a timed current method. Double layer capacitance (Cdl) was measured at cyclic voltammetric scan speeds of 20, 40, 60, 80, 100 mV/s, respectively. The potential was calculated using this formula:
E RHE =E Hg/HgO +0.0592 pH+0.098 V
wherein E is RHE For reversible hydrogen electrode potential (RHE), E Hg/HgO The pH is the pH value of the electrolyte for the Hg/HgO electrode potential.
The preparation method of the OER electrocatalyst in the oxygen evolution reaction comprises the following steps: mix 4 mg perovskite nanofiber catalyst with 340 μl deionized water, 160 μl ethanol and 20 μl Nafion. Ultrasound was applied for 20 minutes, and 100. Mu.L of the obtained uniformly mixed catalyst ink was dropped onto carbon paper (load = 1.538 mg/cm) 2 ) 。
The perovskite nanofiber catalysts were the perovskite nanofiber catalysts prepared in example 1 and example 2, respectively. To compare different doping amounts La 0.9 Pr x Co 0.7 Mn 0.3 O 3 (x=0.1, 0.2) OER activity at saturation O using a three electrode system 2 The test LSV in KOH solution of 1.0M) compares OER performance. The test results are shown in FIG. 5, at 10mA cm -2 La at current density of (1) 0.9 Pr 0.1 Co 0.7 Mn 0.3 O 3 And La (La) 0.9 Pr 0.2 Co 0.7 Mn 0.3 O 3 The overpotential of the catalyst was 404mV and 520 mV, respectively.
Oxygen Reduction Reaction (ORR) activity was also measured using a conventional three-electrode system, each of which was electrically rotated by a GC disk coated with a catalystThe electrode (RDE) was the working electrode (load 0.147 mg/cm) 2 ) Saturated Calomel Electrode (SCE) (sat. KCl) and graphite rod are reference and counter electrodes. The test was performed with a CHI660E electrochemical workstation in 0.1M KOH with saturated oxygen and scanned at a speed of 100 mV/s for 50 cycles prior to the ORR test. Drawing an LSV curve at a scanning rate of 5 mV/s@1600 rpm, and calculating overpotential and electron transfer number according to the formula:
E RHE =E SCE +0.0592 pH+0.098 V
n=4 I d / (I d +I r /N)
wherein E is RHE For reversible hydrogen electrode potential (RHE), E SCE The potential of a reference electrode (calomel electrode), the pH value of the electrolyte is the pH value, n is the electron transfer number of ORR reaction, I d For rotating the electrode disk current of the ring disk, I r The electrode ring current of the rotating ring disk is N, and the collecting efficiency of the rotating ring disk is N.
Oxygen Reduction Reaction (ORR) electrocatalyst preparation step: 1mg of the catalyst sample was mixed with 1mg carbon black, mixed with 340 μl of deionized water, 160 μl of ethanol, and 20 μl of Nafion. Ultrasonic treatment was carried out for 20 minutes, and 15. Mu.L of the obtained catalyst ink uniformly mixed was dropped onto a glassy carbon electrode (load = 0.195 mg/cm) 2 ). The results of the test using the perovskite nanofiber catalyst described in example 1 are shown in fig. 3, and the results of the test using the perovskite nanofiber catalyst described in example 2 are shown in fig. 4. The results show that the perovskite nanofiber catalyst prepared by the invention is used as a working electrode of a three-electrode system, and the LSV curve shows La at 1600 rpm 0.9 Pr 0.1 Co 0.7 Mn 0.3 O 3 Is optimal in ORR performance, has a half-wave potential of 0.42V and a limiting current density of 4.85 mA cm -2 。La 0.9 Pr 0.2 Co 0.7 Mn 0.3 O 3 The half-wave potential of the catalyst is 0.54V, and the limiting current density is 2.36 mA cm -2 。
Experimental example 2
Zinc-air battery assembly and testing
From zinc foil, 6M KOH and Zn (Ac) 2 Electrolyte (17.715 g KOH+ 1.835 g Zn (Ac) 2 + 50 mL H 2 O), whatman TM glass microfiber membrane and nickel foam. The catalyst thus prepared was coated on a gas diffusion layer as a cathode (load 2 mg/cm) 2 ) Zinc sheets are used as anodes. Zinc air cell performance testing was performed using the wuhan koste CS350H electrochemical workstation at room temperature.
The preparation method of the catalyst in the zinc-air battery comprises the following steps: 5mg catalyst sample (example 1) +5 mg carbon black was mixed with 340. Mu.L deionized water, 160. Mu.L ethanol and 20. Mu.L Nafion. Ultrasound was applied for 20 minutes, and 520. Mu.l of the obtained catalyst ink was dropped onto carbon paper (load 2 mg/cm) 2 )。
The catalyst is used as an air cathode catalyst of a zinc-air battery, and the zinc-air battery is self-assembled. Measured by a multimeter in La 0.9 Pr 0.1 Co 0.7 Mn 0.3 O 3 The open circuit voltage of the zinc air cell assembled for the catalyst was 1.360V. By La 0.9 Pr 0.1 Co 0.7 Mn 0.3 O 3 The zinc-air battery air cathode catalyst is used as a zinc-air battery air cathode catalyst, and the small fan and the LED lamp are assembled, so that the small fan can be rotated and the LED lamp can be lightened.
In the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A perovskite nanofiber catalyst is characterized in that the perovskite nanofiber catalyst is La loaded on a carbon fiber framework 0.9 Pr x Co 0.7 Mn 0.3 O 3 Wherein x is 0.1 or 0.2;
the perovskite nanofiber catalyst is prepared by the following steps:
1) Mixing a lanthanum source, a praseodymium source, a cobalt source and a manganese source with an organic solvent to obtain an electrostatic spinning precursor solution;
2) Carrying out electrostatic spinning on the electrostatic spinning precursor solution to obtain a high polymer fiber membrane;
3) Heating a polymer fiber membrane under a protective atmosphere, and then heating the polymer fiber membrane under an air atmosphere to obtain a perovskite nanofiber catalyst;
the heating temperature in the step 3) is 350-450 ℃ and the heating time is 1.5-2.5 h under the protection atmosphere; the heating temperature is 550-650 ℃ and the heating time is 0.8-1.2 h under the air atmosphere.
2. A method of preparing a perovskite nanofiber catalyst as claimed in claim 1, comprising the steps of:
1) Mixing a lanthanum source, a praseodymium source, a cobalt source and a manganese source with an organic solvent to obtain an electrostatic spinning precursor solution;
2) Carrying out electrostatic spinning on the electrostatic spinning precursor solution to obtain a high polymer fiber membrane;
3) And heating the polymer fiber membrane in a protective atmosphere, and then heating the polymer fiber membrane in an air atmosphere to obtain the perovskite nanofiber catalyst.
3. The method for preparing the perovskite nanofiber catalyst according to claim 2, wherein the organic solvent is an N, N-dimethylformamide solution of polyvinylpyrrolidone, and the mass concentration of the organic solvent is 12%.
4. A method for preparing a perovskite nanofiber catalyst according to claim 3, wherein the molar mass ratio of the total amount of lanthanum source, praseodymium source, cobalt source and manganese source to the organic solvent is 1.5-1.575 mmol: 4-8 g.
5. The method according to any one of claims 2 to 4, wherein the mixing in step 1) comprises stirring for a period of 10 to 15 hours at a rate of 250 to 350rpm.
6. The method for preparing a perovskite nanofiber catalyst according to claim 5, wherein the lanthanum source comprises one or more of lanthanum nitrate, lanthanum nitrate hexahydrate, lanthanum carbonate, lanthanum chloride and lanthanum acetate; the praseodymium source comprises one or more of praseodymium nitrate, praseodymium nitrate hexahydrate, praseodymium carbonate, praseodymium chloride and praseodymium sulfate; the cobalt source comprises one or more of cobalt nitrate, cobalt nitrate hexahydrate, cobalt chloride and cobalt sulfate; the manganese source comprises one or more of manganese acetate, manganese sulfate and manganese chloride.
7. The method for preparing a perovskite nanofiber catalyst according to claim 6, wherein the voltage of the electrostatic spinning in the step 2) is 15-18 kV, and the distance of the electrostatic spinning is 12-15 cm.
8. The method for preparing a perovskite nanofiber catalyst according to claim 6 or 7, wherein the heating temperature in the protective atmosphere in the step 3) is 350-450 ℃ and the heating time is 1.5-2.5 h; the heating temperature is 550-650 ℃ and the heating time is 0.8-1.2 h under the air atmosphere.
9. A method of preparing a perovskite nanofibre catalyst according to claim 8, wherein the protective atmosphere comprises a rare gas atmosphere and/or a nitrogen atmosphere.
10. Use of a perovskite nanofiber catalyst prepared by the preparation method of the perovskite nanofiber catalyst according to any one of claims 2-9 in zinc air batteries.
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