CN111910290B - Cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution and preparation method and application thereof - Google Patents
Cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution and preparation method and application thereof Download PDFInfo
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- 229910000990 Ni alloy Inorganic materials 0.000 title claims abstract description 58
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 53
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 50
- 238000009826 distribution Methods 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 66
- 238000000034 method Methods 0.000 claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 11
- 230000003197 catalytic effect Effects 0.000 claims abstract description 7
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 10
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 claims description 9
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 claims description 9
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 7
- 230000000977 initiatory effect Effects 0.000 claims description 3
- 238000011534 incubation Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000630 rising effect Effects 0.000 claims 1
- 238000006722 reduction reaction Methods 0.000 abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 7
- 239000002105 nanoparticle Substances 0.000 abstract description 7
- 229920000049 Carbon (fiber) Polymers 0.000 abstract description 6
- 239000004917 carbon fiber Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 abstract description 3
- 239000010941 cobalt Substances 0.000 abstract description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052759 nickel Inorganic materials 0.000 abstract description 3
- 239000003575 carbonaceous material Substances 0.000 abstract description 2
- 239000003446 ligand Substances 0.000 abstract description 2
- 239000002114 nanocomposite Substances 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 239000002245 particle Substances 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229910052573 porcelain Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000009987 spinning Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000000446 fuel Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002082 metal nanoparticle Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910003266 NiCo Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- B01J35/33—
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- B01J35/40—
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- B01J35/61—
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- 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
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution and a preparation method and application thereof, and belongs to the technical field of nanocomposite preparation. According to the preparation method, reasonable cobalt source, nickel source and carbon-based material precursor are adopted, the propelling speed of the inner shaft and the outer shaft is regulated and controlled through coaxial electrostatic spinning, ethylenediamine is introduced to form a ligand with cobalt-nickel alloy of the outer shaft, cobalt-nickel alloy nanoparticles are formed by the cobalt-nickel alloy and are distributed on the outer layer of the carbon fiber more, gradient structure distribution of the cobalt-nickel alloy nanoparticles on the carbon fiber from inside to outside is realized, active sites are increased, and electrocatalytic performance is improved; meanwhile, pure carbon is used as an inner shaft, so that the flexibility of the material can be increased, the stability of the composite material is improved, and the applicability of the obtained material is improved. Therefore, the cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution prepared by the method has good electrical property and service performance, and can be applied to an oxygen reduction reaction catalytic electrode.
Description
Technical Field
The invention belongs to the technical field of nano composite material preparation, and relates to a cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution, and a preparation method and application thereof.
Background
Due to the rapid development of society, energy demands are increasing. While the resulting climate change and environmental problems are pushing scientists to seek sustainable and environmentally friendly alternative energy sources to replace increasingly depleted fossil fuels. The hydrogen fuel cell directly converts chemical energy into electric energy, has high energy conversion rate (40-60%), no pollution in the process, can solve the problems of energy shortage, environmental pollution and the like, and has wide application prospect.
Oxygen Reduction Reactions (ORR) and Oxygen Evolution Reactions (OER) are two important half reactions in hydrogen fuel cells. The cathodic oxygen reduction (ORR) process involves one or more four electron transfer reactions, which are extremely slow in kinetics, which can lead to excessive potential and possibly excessive hydrogen peroxide generation, thereby greatly reducing the conversion efficiency of the fuel cell. Catalysts play a key role in their conversion efficiency, and noble metals, such as Pt, have traditionally been highly catalytically active. However, their scarcity and poor stability limit large-scale applications. Therefore, development of an electrocatalyst which does not contain noble metals and has good stability and catalytic performance is still urgent. Heretofore, various non-noble metals such as cobalt, iron, nickel, etc. have been developed as oxygen electrocatalysts. Especially, the two metals are compounded, and the synergistic effect between the two metals is more beneficial to the catalytic reaction. However, these non-noble metals have high surface energy, which tends to cause particle agglomeration, reduce specific surface area, and limit catalytic activity. Therefore, it is desirable to design a composite electrocatalyst with a specific structure to improve this problem and to improve the electrocatalyst performance.
The literature [ Yue Fu, hai-Yang Yu, cong Jiang, et al NiCo Alloy Nanoparticles Decorated on N-doped Carbon Nanofibers as Highly Active and Durable Oxygen Electrocatalyst [ J ]. Advanced Functional Materials,2017,28 (9) ] successfully prepares a composite material NiCo@N-C through electrostatic spinning and a subsequent heat treatment process, explores the influence of the addition amount of metal salt in a precursor solution on the structure of the composite material, and finally ensures that metal nano particles are uniformly distributed on carbon fibers and have electrocatalytic performance superior to commercial Pt/C. However, the metal nano-particles have large particle size and small specific surface area, so that the number of exposed active sites is small, and the electrocatalytic performance needs to be further improved.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution, and the preparation method and the application thereof.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:
the invention discloses a preparation method of a cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution, which comprises the following steps:
1) Dissolving cobalt acetate tetrahydrate, nickel acetate tetrahydrate, polyacrylonitrile and ethylenediamine in a good solvent to obtain a precursor solution A; dissolving polyacrylonitrile in a good solvent to obtain a precursor liquid B; carrying out coaxial electrostatic spinning on the precursor solution A and the precursor solution B to obtain a precursor;
2) Carrying out heat treatment on the precursor obtained in the step 1) to obtain a cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution;
the gradient distribution structure of the cobalt-nickel alloy/carbon composite electrocatalyst is realized by adjusting the propelling speeds of the precursor liquid A and the precursor liquid B.
Preferably, in the step 1), when preparing the precursor solution A, the reaction feeding ratio of cobalt acetate tetrahydrate, nickel acetate tetrahydrate, polyacrylonitrile, ethylenediamine and good solvent is (1-2) mmol (0.5-1) mmol (0.6-0.8) g (1-2) mL (8-10) mL; when preparing the precursor solution B, the reaction feeding ratio of the polyacrylonitrile and the good solvent is (0.6-0.8) g (8-10) mL.
Preferably, in the step 1), the voltage of the coaxial electrostatic spinning operation is 15-17 kV, the propelling speed is 1-3 mm/h, and the rotating speed of the roller is 300-400 r/min.
Preferably, in step 1), the precursor solution a is used as an outer shaft and the precursor solution B is used as an inner shaft in the coaxial electrospinning operation.
Preferably, in step 1), the good solvent is N, N-dimethylformamide or dimethyl sulfoxide.
Preferably, the reaction temperature of the heat treatment in the step 2) is 500-800 ℃, the heat preservation time is 1-2 h, and the heating rate is 3-5 ℃/min.
Preferably, in step 2), the reaction conditions of the heat treatment are in an inert atmosphere or under vacuum.
The invention also discloses the cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution prepared by the preparation method.
Preferably, the cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution has an oxygen reduction initiation potential of 0.92V.
The invention also discloses application of the cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution as an oxygen reduction reaction catalytic electrode.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of a cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution, which adopts a reasonable cobalt source, a nickel source and a carbon-based material precursor, regulates and controls the propelling speed of an inner shaft and an outer shaft through coaxial electrostatic spinning, and forms a ligand with the cobalt-nickel alloy of the outer shaft through introducing ethylenediamine, thereby being beneficial to forming cobalt-nickel alloy nano particles by the cobalt-nickel alloy and being distributed on the outer layer of carbon fiber more, realizing the gradient structure distribution of metal nano particles (cobalt-nickel alloy nano particles) on the carbon fiber from inside to outside, and improving the electrocatalysis performance of the cobalt-nickel alloy/carbon composite electrocatalyst while exposing more active sites. Meanwhile, pure Polyacrylonitrile (PAN) is used as an inner shaft, so that the flexibility of the composite material can be improved, the stability of the composite material can be improved, and the applicability of the finally obtained material is improved.
The invention also discloses the cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution, which is prepared by adopting the preparation method, and the coaxial electrostatic spinning method is used for preparing the composite material with the cobalt-nickel alloy nanoparticle gradient distribution structure, so that more active sites are exposed, and the prepared cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution has high specific surface area and good conductivity, and improves the utilization rate of the electrocatalyst; meanwhile, pure carbon is used as an inner shaft to increase the flexibility of the material and improve the stability of the composite material. Related tests show that the nano cobalt-nickel alloy particles in the cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution have the size of about 5-7 nm, and have uniform morphology and good dispersibility; the cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution has good electrical property and service performance.
The invention also discloses application of the cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution as an oxygen reduction reaction catalytic electrode. Related tests show that the cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution disclosed by the invention has the oxygen reduction initiation potential of 0.92V, and in the material structure, the utilization rate of the electrocatalyst is improved by inhibiting agglomeration of particles, exposing more active particles and increasing specific surface area, so that the cobalt-nickel alloy/carbon composite electrocatalyst has high application value in the use of an oxygen reduction reaction catalytic electrode.
Drawings
FIG. 1 is a schematic diagram of the preparation and structure of a cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution according to the invention;
FIG. 2 is an XRD pattern of a cobalt-nickel alloy/carbon composite electrocatalyst having a gradient profile prepared in example 1, example 2, example 3 according to the invention;
FIG. 3 is an SEM image of a cobalt nickel alloy/carbon composite electrocatalyst having a gradient profile prepared in example 2 according to the invention; wherein, (a) is 1.5mm/h-3mm/h low power; (b) is 1.5mm/h-3mm/h high power;
fig. 4 is an LSV plot of the cobalt nickel alloy/carbon composite electrocatalyst with gradient profile prepared in example 1, example 2, example 3 according to the invention.
Detailed Description
In order that those skilled in the art will better understand the present invention, a technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in which it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and the claims of the present invention and the above figures are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged where appropriate such that the embodiments of the invention described herein may be implemented in sequences other than those illustrated or otherwise described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
Example 1
Step one: 2mmol of cobalt acetate tetrahydrate, 1mmol of nickel acetate tetrahydrate, 0.8g of polyacrylonitrile and 2mL of ethylenediamine are weighed, dissolved in 10mLN, N-dimethylformamide and stirred for 12 hours to obtain a precursor solution A; 0.8g of polyacrylonitrile is weighed, dissolved in 10mLN, N-dimethylformamide and stirred for 12 hours to obtain a precursor solution B;
step two: and (3) spinning the precursor solution prepared in the step (A) through a coaxial electrostatic spinning method. The precursor solution A is used as an outer shaft, the propelling speed is 3mm/h, the precursor solution B is used as an inner shaft, and the propelling speed is 1mm/h. The voltage is 17kV, and the rotating speed of the roller is 300r/min. Obtaining the precursor.
Step three: transferring the precursor prepared in the second step into a porcelain boat, reacting in a tubular furnace taking argon as an atmosphere, heating at a rate of 5 ℃/min, maintaining at a temperature of 700 ℃ for 2 hours, and cooling to obtain the cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution.
Example 2
Step one: 2mmol of cobalt acetate tetrahydrate, 1mmol of nickel acetate tetrahydrate, 0.8g of polyacrylonitrile and 2mL of ethylenediamine are weighed, dissolved in 10mLN, N-dimethylformamide and stirred for 12 hours to obtain a precursor solution A; 0.8g of polyacrylonitrile is weighed, dissolved in 10mLN, N-dimethylformamide and stirred for 12 hours to obtain a precursor solution B;
step two: and (3) spinning the precursor solution prepared in the step (A) through a coaxial electrostatic spinning method. The precursor solution A is used as an outer shaft, the propelling speed is 1.5mm/h, the precursor solution B is used as an inner shaft, and the propelling speed is 3mm/h. The voltage is 17kV, and the rotating speed of the roller is 300r/min. Obtaining the precursor.
Step three: transferring the precursor prepared in the second step into a porcelain boat, reacting in a tubular furnace taking argon as an atmosphere, heating at a rate of 5 ℃/min, maintaining at a temperature of 700 ℃ for 2 hours, and cooling to obtain the cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution.
Example 3
Step one: 2mmol of cobalt acetate tetrahydrate, 1mmol of nickel acetate tetrahydrate, 0.8g of polyacrylonitrile and 2mL of ethylenediamine are weighed, dissolved in 10mLN, N-dimethylformamide and stirred for 12 hours to obtain a precursor solution A; 0.8g of polyacrylonitrile is weighed, dissolved in 10mLN, N-dimethylformamide and stirred for 12 hours to obtain a precursor solution B;
step two: and (3) spinning the precursor solution prepared in the step (A) through a coaxial electrostatic spinning method. The precursor solution A is used as an outer shaft, the propelling speed is 3mm/h, the precursor solution B is used as an inner shaft, and the propelling speed is 3mm/h. The voltage is 17kV, and the rotating speed of the roller is 300r/min. Obtaining the precursor.
Step three: transferring the precursor prepared in the second step into a porcelain boat, reacting in a tubular furnace taking argon as an atmosphere, heating at a rate of 5 ℃/min, maintaining at a temperature of 700 ℃ for 2 hours, and cooling to obtain the cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution.
Example 4
Step one: 1mmol of cobalt acetate tetrahydrate, 0.5mmol of nickel acetate tetrahydrate, 0.6g of polyacrylonitrile and 1mL of ethylenediamine are weighed, dissolved in 8mL of dimethyl sulfoxide and stirred for 12 hours to obtain a precursor solution A; weighing 0.6g of polyacrylonitrile, dissolving the polyacrylonitrile in 8mL of dimethyl sulfoxide, and stirring for 12h to obtain a precursor solution B;
step two: and (3) spinning the precursor solution prepared in the step (A) through a coaxial electrostatic spinning method. The precursor solution A is used as an outer shaft, the propelling speed is 1mm/h, the precursor solution B is used as an inner shaft, and the propelling speed is 1mm/h. The voltage is 15kV, and the rotating speed of the roller is 330r/min. Obtaining the precursor.
Step three: transferring the precursor prepared in the second step into a porcelain boat, reacting in a tubular furnace taking argon as an atmosphere, heating at a rate of 3 ℃/min, maintaining at 500 ℃ for 1h, and cooling to obtain the cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution.
Example 5
Step one: 1.4mmol of cobalt acetate tetrahydrate, 0.7mmol of nickel acetate tetrahydrate, 0.7g of polyacrylonitrile and 1.5mL of ethylenediamine are weighed, dissolved in 9mL of dimethyl sulfoxide and stirred for 12 hours to obtain a precursor solution A; weighing 0.7g of polyacrylonitrile, dissolving the polyacrylonitrile in 9mL of dimethyl sulfoxide, and stirring for 12h to obtain a precursor solution B;
step two: and (3) spinning the precursor solution prepared in the step (A) through a coaxial electrostatic spinning method. The precursor solution A is used as an outer shaft, the propelling speed is 2mm/h, the precursor solution B is used as an inner shaft, and the propelling speed is 2mm/h. The voltage is 16kV, and the rotating speed of the roller is 400r/min. Obtaining the precursor.
Step three: transferring the precursor prepared in the second step into a porcelain boat, reacting in a tubular furnace taking argon as an atmosphere, heating at a rate of 4 ℃/min, maintaining at 800 ℃ for 1.5 hours, and cooling to obtain the cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution.
In the above examples, the heat treatment was performed under inert gas or vacuum conditions to prevent oxidation, so as to obtain the objective product.
The invention is described in further detail below with reference to the attached drawing figures:
referring to fig. 1, in order to provide a schematic diagram of a preparation device and a structure of a cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution, a precursor solution a and a precursor solution B are respectively installed in two injectors, wherein the injector with the precursor solution a is connected with an outer shaft of a coaxial electrostatic spinning head, the injector with the precursor solution B is connected with an inner shaft of the coaxial electrostatic spinning head, and the cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution is finally obtained by controlling the advancing speeds of the two injectors. The cobalt-nickel alloy/carbon composite electrocatalyst consists of pure carbon (an inner layer) and cobalt-nickel alloy (an outer layer) distributed on carbon fibers, and the special structure is beneficial to improving the electrocatalytic efficiency and stability.
Referring to fig. 2, the XRD patterns of the cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution prepared in the example of the invention can be seen from the figure that the standard PDF card numbers corresponding to the samples are Co 15-0806 and Ni 04-0850, indicating that the carbon-based cobalt-nickel alloy composite material was successfully prepared.
Referring to fig. 3, an SEM spectrum of a cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution prepared by the embodiment of the invention shows that the prepared composite material has small particle size and large number of nano particles and is distributed in a gradient manner, so that the structure is favorable for performing an electrocatalytic oxygen reduction reaction and the utilization rate of the catalyst can be improved.
Referring to FIG. 4, an LSV spectrum of the cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution prepared in the example of the invention shows that the composite material prepared at the advancing speed of 1.5mm/h-3mm/h of the inner and outer axes has the best electrocatalytic oxygen reduction performance, and the oxygen reduction initial potential reaches 0.92V.
The above is only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited by this, and any modification made on the basis of the technical scheme according to the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (7)
1. The preparation method of the cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution is characterized by comprising the following steps:
1) Dissolving cobalt acetate tetrahydrate, nickel acetate tetrahydrate, polyacrylonitrile and ethylenediamine in a good solvent to obtain a precursor solution A; dissolving polyacrylonitrile in a good solvent to obtain a precursor liquid B; carrying out coaxial electrostatic spinning on the precursor solution A and the precursor solution B to obtain a precursor;
2) Carrying out heat treatment on the precursor obtained in the step 1) to obtain a cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution;
the gradient distribution structure of the cobalt-nickel alloy/carbon composite electrocatalyst is realized by adjusting the propelling speeds of the precursor liquid A and the precursor liquid B;
in the step 1), the voltage of coaxial electrostatic spinning operation is 15-17 kV, the propelling speed is 1-3 mm/h, and the rotating speed of a roller is 300-400 r/min;
in the step 1), in the coaxial electrostatic spinning operation, the precursor liquid A is used as an outer shaft, and the precursor liquid B is used as an inner shaft;
in the step 1), the good solvent is N, N-dimethylformamide or dimethyl sulfoxide.
2. The method for preparing the cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution according to claim 1, wherein in step 1), when preparing the precursor solution a, the reaction feed ratio of cobalt acetate tetrahydrate, nickel acetate tetrahydrate, polyacrylonitrile, ethylenediamine and good solvent is (1-2) mmol (0.5-1) mmol (0.6-0.8) g (1-2) mL (8-10) mL; when preparing the precursor solution B, the reaction feeding ratio of the polyacrylonitrile and the good solvent is (0.6-0.8) g (8-10) mL.
3. The method of cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution according to claim 1, wherein the reaction temperature of the heat treatment in step 2) is 500 to 800 ℃, the incubation time is 1 to 2 hours, and the temperature rising rate is 3 to 5 ℃/min.
4. The method of cobalt nickel alloy/carbon composite electrocatalyst with gradient distribution according to claim 1, wherein in step 2), the reaction conditions of the heat treatment are inert atmosphere or vacuum conditions.
5. A cobalt-nickel alloy/carbon composite electrocatalyst having gradient distribution, produced by the production method according to any one of claims 1 to 4.
6. The cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution according to claim 5, wherein the cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution has an oxygen reduction initiation potential capable of reaching 0.92V.
7. Use of the cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution according to claim 5 or 6 as an oxygen reduction catalytic electrode.
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