CN111910290A - 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 61
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 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 52
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 52
- 238000009826 distribution Methods 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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 15
- 238000006722 reduction reaction Methods 0.000 claims abstract description 13
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 12
- 230000003197 catalytic effect Effects 0.000 claims abstract description 8
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 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 13
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 claims description 13
- 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 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
- 230000009467 reduction Effects 0.000 claims description 6
- 238000001523 electrospinning Methods 0.000 claims description 5
- 230000000977 initiatory effect Effects 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims 2
- 239000002105 nanoparticle Substances 0.000 abstract description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 7
- 229920000049 Carbon (fiber) Polymers 0.000 abstract description 6
- 239000004917 carbon fiber Substances 0.000 abstract description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 4
- 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
- 230000002349 favourable effect Effects 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
- 238000004321 preservation Methods 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000002245 particle Substances 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
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 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
- 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
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011852 carbon nanoparticle Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001228 spectrum 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
-
- B01J35/33—
-
- B01J35/40—
-
- B01J35/61—
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- Y02E60/30—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, belonging to the technical field of nano composite material preparation. The preparation method adopts reasonable cobalt source, nickel source and carbon-based material precursor, regulates the propelling speed of the inner shaft and the outer shaft through coaxial electrostatic spinning, and forms a ligand with the cobalt-nickel alloy of the outer shaft through introducing ethylenediamine, so that the cobalt-nickel alloy is favorable for forming cobalt-nickel alloy nano particles and more cobalt-nickel alloy nano particles are distributed on the outer layer of the carbon fiber, the gradient structure distribution of the cobalt-nickel alloy nano particles on the carbon fiber from inside to outside is realized, active sites are increased, and the electrocatalysis performance is improved; meanwhile, pure carbon is used as an inner shaft, so that the flexibility of the material can be improved, 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 catalytic electrodes of oxygen reduction reactions.
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 demand is increasing. The resulting climate change and environmental issues are driving scientists to seek sustainable and environmentally friendly alternative energy sources to replace the ever-depleting fossil fuels. The hydrogen fuel cell directly converts chemical energy into electric energy, has high energy conversion rate (40-60%), has no pollution in the process, can solve the problems of energy shortage, environmental pollution and the like, and has wide application prospect.
The Oxygen Reduction Reaction (ORR) and the Oxygen Evolution Reaction (OER) are two important half-reactions in hydrogen fuel cells. The cathodic oxygen reduction (ORR) process involves one or more four-electron transfer reactions with extremely slow kinetics that can lead to excessive potentials and possibly excessive hydrogen peroxide production, thereby greatly reducing the conversion efficiency of the fuel cell. The catalyst plays a key role in its conversion efficiency, and conventionally, noble metals, such as Pt, have high catalytic activity. However, their scarcity and poor stability limit large-scale applications. Therefore, there is still a need to develop electrocatalysts which are free of noble metals and have good stability and catalytic properties. Heretofore, various non-noble metals, such as cobalt, iron, nickel, etc., have been developed as oxygen electrocatalysts. Particularly, two metals are compounded, and the synergistic effect between the two metals is more beneficial to the catalytic reaction. However, these non-noble metals, due to their high surface energy, tend to cause particle agglomeration and reduce the specific surface area, thereby limiting the catalytic activity. Therefore, it is necessary to design a composite electrocatalyst with a special structure to improve this problem and enhance the electrocatalytic performance.
The document [ Yue Fu, Hai-Yang Yu, Cong Jiang, et al, NiCo Alloy Nanoparticles purified on N-doped Carbon Nanoparticles as high Active and Durable Oxygen electrochemical analysis [ J ]. Advanced Functional Materials,2017,28(9) ] successfully prepares the composite material NiCo @ N-C through electrostatic spinning and subsequent heat treatment processes, and researches the influence of the addition amount of metal salt in the precursor liquid on the structure of the composite material, so that the metal Nanoparticles are uniformly distributed on the Carbon fiber finally, and the electrocatalytic performance of the composite material is better than that of commercial Pt/C. However, the metal nanoparticles 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 a cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
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 precursor;
2) carrying out heat treatment on the protofilament obtained in the step 1) to obtain a cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution;
wherein, 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 the precursor solution A is prepared, the reaction charge 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 the precursor liquid B is prepared, the reaction charge ratio of polyacrylonitrile and a 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 advancing speed is 1-3 mm/h, and the rotating speed of the roller is 300-400 r/min.
Preferably, in step 1), the coaxial electrospinning operation is performed with the front driving liquid a as the outer shaft and the front driving liquid B as the inner shaft.
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 a 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 oxygen reduction initiation potential reaching 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 the propelling speed of an inner shaft and an outer shaft through coaxial electrostatic spinning, and forms a ligand with a cobalt-nickel alloy of the outer shaft by introducing ethylenediamine, so that the cobalt-nickel alloy is favorable for forming cobalt-nickel alloy nanoparticles and more nanoparticles are distributed on the outer layer of carbon fibers, the gradient structure distribution of metal nanoparticles (cobalt-nickel alloy nanoparticles) on the carbon fibers from inside to outside is realized, and the electrocatalytic performance of the cobalt-nickel alloy/carbon composite electrocatalyst is improved while more active sites are exposed. Meanwhile, pure Polyacrylonitrile (PAN) serving as an inner shaft can not only increase the flexibility of the composite material, but also improve the stability of the composite material, so that the applicability of the finally obtained material is improved.
The invention also discloses the cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution prepared by the preparation method, and the invention can prepare the composite material with a cobalt-nickel alloy nanoparticle gradient distribution structure by using a coaxial electrostatic spinning method, thereby exposing more active sites, 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, so that the flexibility of the material is increased, and the stability of the composite material is improved. Relevant tests show that the size of nano cobalt-nickel alloy particles in the cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution is about 5-7 nm, the morphology is uniform, and the dispersibility is good; the obtained 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. Relevant tests show that the oxygen reduction initial potential of the cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution disclosed by the invention can reach 0.92V, and in the material structure, the utilization rate of the electrocatalyst is improved by inhibiting the agglomeration of particles, exposing more active particles and increasing the 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 present invention;
FIG. 2 is an XRD pattern of a cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution prepared in example 1, example 2, and example 3 according to the present invention;
FIG. 3 is an SEM image of a cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution prepared in example 2 of the present invention; wherein (a) is 1.5mm/h-3 mm/h; (b) 1.5mm/h-3mm/h high power;
fig. 4 is a LSV curve of the cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution prepared in example 1, example 2, and example 3 according to the present invention.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or 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
The method comprises the following steps: weighing 2mmol of cobalt acetate tetrahydrate, 1mmol of nickel acetate tetrahydrate, 0.8g of polyacrylonitrile and 2mL of ethylenediamine, dissolving the cobalt acetate tetrahydrate, the nickel acetate tetrahydrate, the polyacrylonitrile and the ethylenediamine in 10mLN, N-dimethylformamide, and stirring for 12 hours to obtain a precursor solution A; weighing 0.8g of polyacrylonitrile, dissolving the polyacrylonitrile in 10mLN, N-dimethylformamide, and stirring for 12 hours to obtain a precursor solution B;
step two: and (4) spinning the precursor solution prepared in the step one by a coaxial electrostatic spinning method. The advancing speed of the precursor liquid A as an outer shaft is 3mm/h, and the advancing speed of the precursor liquid B as an inner shaft is 1 mm/h. The voltage is 17kV, and the rotating speed of the roller is 300 r/min. And (4) obtaining the protofilament.
Step three: transferring the protofilament prepared in the second step into a porcelain boat, reacting in a tubular furnace with argon as atmosphere, wherein the heating rate is 5 ℃/min, the heat preservation temperature is 700 ℃, the heat preservation time is 2h, and cooling to obtain the cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution.
Example 2
The method comprises the following steps: weighing 2mmol of cobalt acetate tetrahydrate, 1mmol of nickel acetate tetrahydrate, 0.8g of polyacrylonitrile and 2mL of ethylenediamine, dissolving the cobalt acetate tetrahydrate, the nickel acetate tetrahydrate, the polyacrylonitrile and the ethylenediamine in 10mLN, N-dimethylformamide, and stirring for 12 hours to obtain a precursor solution A; weighing 0.8g of polyacrylonitrile, dissolving the polyacrylonitrile in 10mLN, N-dimethylformamide, and stirring for 12 hours to obtain a precursor solution B;
step two: and (4) spinning the precursor solution prepared in the step one by a coaxial electrostatic spinning method. The advancing speed of the precursor liquid A as an outer shaft is 1.5mm/h, and the advancing speed of the precursor liquid B as an inner shaft is 3 mm/h. The voltage is 17kV, and the rotating speed of the roller is 300 r/min. And (4) obtaining the protofilament.
Step three: transferring the protofilament prepared in the second step into a porcelain boat, reacting in a tubular furnace with argon as atmosphere, wherein the heating rate is 5 ℃/min, the heat preservation temperature is 700 ℃, the heat preservation time is 2h, and cooling to obtain the cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution.
Example 3
The method comprises the following steps: weighing 2mmol of cobalt acetate tetrahydrate, 1mmol of nickel acetate tetrahydrate, 0.8g of polyacrylonitrile and 2mL of ethylenediamine, dissolving the cobalt acetate tetrahydrate, the nickel acetate tetrahydrate, the polyacrylonitrile and the ethylenediamine in 10mLN, N-dimethylformamide, and stirring for 12 hours to obtain a precursor solution A; weighing 0.8g of polyacrylonitrile, dissolving the polyacrylonitrile in 10mLN, N-dimethylformamide, and stirring for 12 hours to obtain a precursor solution B;
step two: and (4) spinning the precursor solution prepared in the step one by a coaxial electrostatic spinning method. The precursor liquid A is used as an outer shaft, the advancing speed is 3mm/h, the precursor liquid B is used as an inner shaft, and the advancing speed is 3 mm/h. The voltage is 17kV, and the rotating speed of the roller is 300 r/min. And (4) obtaining the protofilament.
Step three: transferring the protofilament prepared in the second step into a porcelain boat, reacting in a tubular furnace with argon as atmosphere, wherein the heating rate is 5 ℃/min, the heat preservation temperature is 700 ℃, the heat preservation time is 2h, and cooling to obtain the cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution.
Example 4
The method comprises the following steps: weighing 1mmol of cobalt acetate tetrahydrate, 0.5mmol of nickel acetate tetrahydrate, 0.6g of polyacrylonitrile and 1mL of ethylenediamine, dissolving the cobalt acetate tetrahydrate, the nickel acetate tetrahydrate and the polyacrylonitrile and the ethylenediamine in 8mL of dimethyl sulfoxide, and stirring 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 12 hours to obtain a precursor solution B;
step two: and (4) spinning the precursor solution prepared in the step one by a coaxial electrostatic spinning method. The advancing speed of the precursor liquid A as an outer shaft is 1mm/h, and the advancing speed of the precursor liquid B as an inner shaft is 1 mm/h. The voltage is 15kV, and the rotating speed of the roller is 330 r/min. And (4) obtaining the protofilament.
Step three: transferring the protofilament prepared in the second step into a porcelain boat, reacting in a tubular furnace with argon as atmosphere, wherein the heating rate is 3 ℃/min, the heat preservation temperature is 500 ℃, the heat preservation time is 1h, and cooling to obtain the cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution.
Example 5
The method comprises the following steps: weighing 1.4mmol of cobalt acetate tetrahydrate, 0.7mmol of nickel acetate tetrahydrate, 0.7g of polyacrylonitrile and 1.5mL of ethylenediamine, dissolving the mixture in 9mL of dimethyl sulfoxide, and stirring 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 12 hours to obtain a precursor solution B;
step two: and (4) spinning the precursor solution prepared in the step one by a coaxial electrostatic spinning method. The precursor liquid A is used as an outer shaft, the advancing speed is 2mm/h, the precursor liquid B is used as an inner shaft, and the advancing speed is 2 mm/h. The voltage is 16kV, and the rotating speed of the roller is 400 r/min. And (4) obtaining the protofilament.
Step three: transferring the protofilament prepared in the second step into a porcelain boat, reacting in a tubular furnace with argon as atmosphere, wherein the heating rate is 4 ℃/min, the heat preservation temperature is 800 ℃, the heat preservation time is 1.5h, and cooling to obtain the cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution.
In the above examples, the heat treatment is performed under an inert gas atmosphere or under vacuum to prevent oxidation, so as to obtain the target product.
The invention is described in further detail below with reference to the accompanying drawings:
referring to fig. 1, a schematic diagram of a preparation apparatus and a structure of the cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution according to the present invention is that a precursor solution a and a precursor solution B are respectively installed in two injectors, wherein the injector containing the precursor solution a is connected to an outer shaft of a coaxial electrospinning head, the injector containing the precursor solution B is connected to an inner shaft of the coaxial electrospinning head, and the cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution is finally obtained by controlling the propelling speeds of the two injectors. The cobalt-nickel alloy/carbon composite electrocatalyst is composed of pure carbon (inner layer) and cobalt-nickel alloy (outer layer) distributed on carbon fiber, and the special structure is favorable for improving the electrocatalytic efficiency and stability.
Referring to fig. 2, an XRD pattern of the cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution prepared in the example of the present invention can be seen from the pattern that the standard PDF card numbers Co 15-0806 and Ni 04-0850 correspond to the sample, indicating that the carbon-based cobalt-nickel alloy composite material was successfully prepared.
Referring to fig. 3, an SEM image of the cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution prepared in the embodiment of the present invention shows that, through analysis, the prepared composite material has small and numerous nanoparticles in gradient distribution, such a structure is beneficial to the implementation of the electrocatalytic oxygen reduction reaction, and the utilization rate of the catalyst can be improved.
Referring to fig. 4, it can be seen from the comparative analysis that the LSV spectrum of the cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution prepared in the embodiment of the present invention shows that the composite material prepared with the inner and outer shafts at the advancing speed of 1.5mm/h to 3mm/h has the best electrocatalytic oxygen reduction performance, and the initial oxygen reduction potential reaches 0.92V.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. A preparation method of a 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 precursor;
2) carrying out heat treatment on the protofilament obtained in the step 1) to obtain a cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution;
wherein, 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.
2. The preparation method of the cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution according to claim 1, wherein in the step 1), when the precursor solution A is prepared, the reaction charge 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 the precursor liquid B is prepared, the reaction charge ratio of polyacrylonitrile and a good solvent is (0.6-0.8) g (8-10) mL.
3. The method for preparing a cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution according to claim 1, wherein in step 1), the voltage of the coaxial electrospinning operation is 15-17 kV, the propelling speed is 1-3 mm/h, and the roller rotation speed is 300-400 r/min.
4. The method for preparing a cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution according to claim 1, wherein in step 1), the inner shaft is the front flooding fluid B and the front flooding fluid a is the outer shaft in the coaxial electrospinning operation.
5. The method for preparing a cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution according to claim 1, wherein in step 1), the good solvent is N, N-dimethylformamide or dimethyl sulfoxide.
6. The method of claim 1, wherein the reaction temperature of the heat treatment in the step 2) is 500-800 ℃, the holding time is 1-2 h, and the heating rate is 3-5 ℃/min.
7. The method of preparing a cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution according to claim 1, wherein the reaction condition of the heat treatment in step 2) is in inert atmosphere or under vacuum condition.
8. The cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution prepared by the preparation method of any one of claims 1 to 7.
9. The cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution according to claim 8, wherein the cobalt-nickel alloy/carbon composite electrocatalyst with gradient distribution has oxygen reduction initiation potential up to 0.92V.
10. Use of the cobalt nickel alloy/carbon composite electrocatalyst with gradient distribution according to claim 8 or 9 as catalytic electrode for oxygen reduction reaction.
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