CN113964334A - FeCoCuZnNi composite CNTs material and preparation method thereof - Google Patents
FeCoCuZnNi composite CNTs material and preparation method thereof Download PDFInfo
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- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 43
- 239000000463 material Substances 0.000 title claims abstract description 33
- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000010438 heat treatment Methods 0.000 claims abstract description 35
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 11
- 239000010941 cobalt Substances 0.000 claims abstract description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- 239000010949 copper Substances 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 11
- 239000011701 zinc Substances 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- 238000004108 freeze drying Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 7
- 238000005303 weighing Methods 0.000 claims abstract description 7
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 17
- 239000012300 argon atmosphere Substances 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- 239000004570 mortar (masonry) Substances 0.000 claims description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 3
- 229940044175 cobalt sulfate Drugs 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
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 3
- UEUDBBQFZIMOQJ-UHFFFAOYSA-K ferric ammonium oxalate Chemical compound [NH4+].[NH4+].[NH4+].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O UEUDBBQFZIMOQJ-UHFFFAOYSA-K 0.000 claims description 3
- 229960002413 ferric citrate Drugs 0.000 claims description 3
- 229960002089 ferrous chloride Drugs 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 claims description 3
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 claims description 3
- 229940118149 zinc sulfate monohydrate Drugs 0.000 claims description 3
- RNZCSKGULNFAMC-UHFFFAOYSA-L zinc;hydrogen sulfate;hydroxide Chemical compound O.[Zn+2].[O-]S([O-])(=O)=O RNZCSKGULNFAMC-UHFFFAOYSA-L 0.000 claims description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 229940045803 cuprous chloride Drugs 0.000 claims description 2
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 238000000703 high-speed centrifugation Methods 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 claims description 2
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- OSOVKCSKTAIGGF-UHFFFAOYSA-N [Ni].OOO Chemical compound [Ni].OOO OSOVKCSKTAIGGF-UHFFFAOYSA-N 0.000 claims 1
- 229910000483 nickel oxide hydroxide Inorganic materials 0.000 claims 1
- 229920000049 Carbon (fiber) Polymers 0.000 abstract description 2
- 239000004917 carbon fiber Substances 0.000 abstract description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 29
- 239000006185 dispersion Substances 0.000 description 8
- 230000007547 defect Effects 0.000 description 6
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- 150000001721 carbon Chemical group 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 229940010514 ammonium ferrous sulfate Drugs 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
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
-
- 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 FeCoCuZnNi composite CNTs material and a preparation method thereof, wherein the preparation method comprises the following steps: weighing an iron source, a cobalt source, a copper source, a zinc source, a nickel source and a carbon source according to the weight ratio of atomic substances, dispersing and mixing, and taking out to obtain a mixture A; placing the mixture A in a high-temperature tube furnace, rapidly heating to 140-200 ℃ at a heating rate of 15-30 ℃/min under an inert gas atmosphere, preserving heat for 0.5-1 h, cooling to room temperature, and taking out to obtain a product B; grinding the product B, and then putting the ground solid powder into a freeze drying box for standing; then placing the carbon fiber into a high-temperature tube furnace, rapidly heating to 700-800 ℃ at a heating rate of 10-30 ℃/min in an inert gas atmosphere, cooling to room temperature after heating, and taking out to obtain a product C, namely the FeCoCuZnNi composite CNTs material; the FeCoCuZnNi composite CNTs material prepared by the invention has the advantages of stable structure, good cycle performance and simple preparation method.
Description
Technical Field
The invention belongs to the technical field of composite materials, relates to a composite material and a preparation method thereof, and particularly relates to a combined FeCoCuZnNi composite CNTs material and a preparation method thereof.
Background
The transition metal has a higher theoretical capacity and excellent electrochemical properties in the battery. However, the transition metal itself has some defects that greatly hinder the application of the transition metal as an electrode in a battery, and the defects generally comprise large volume change, poor cycle performance and the like in the process of sodium extraction.
Carbon Nanotubes (CNTs) are a one-dimensional quantum material with a special structure, and CNTs can be simply described as a tubular structure formed by curling interconnected carbon atom layers, and have outstanding properties in mechanical, electrical, magnetic, thermodynamic, and other aspects, including high mechanical strength, elastic modulus, thermal conductivity, electrical conductivity, and the like. The carbon nano tube has great strength and great length-diameter ratio, so that the carbon nano tube is expected to be made into carbon fiber with excellent toughness, the carbon nano tube can be produced in batches at relatively low cost, has excellent performance and wide application prospect, attracts the attention of a large number of researchers for a long time, draws wide attention in academic research and industrial fields, and has great progress in the aspects of preparation and application of the carbon nano tube after long-term research. The research on the growth mechanism of the carbon nanotube preparation method is not deep enough, so that most of the prepared carbon nanotubes are free to orient, randomly distributed and uneven in length and pipe diameter distribution, and the prepared carbon nanotubes serving as a battery anode material have an unstable structure and unsatisfactory conductivity in the charging and discharging processes.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a FeCoCuZnNi composite CNTs material and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of FeCoCuZnNi composite CNTs material comprises the following steps:
the method comprises the following steps: weighing an iron source, a cobalt source, a copper source, a zinc source, a nickel source and a carbon source according to the weight ratio of atomic substances (0.1-1) to (5-20) to (20-50), mixing, and then centrifuging at a high speed to obtain a mixture A;
step two: placing the mixture A in a high-temperature tube furnace, rapidly heating the mixture A to 140-200 ℃ from room temperature at a heating rate of 15-30 ℃/min in an inert gas atmosphere, preserving heat for 0.5-1 h, naturally cooling to room temperature after heat preservation is finished, and taking out to obtain a product B;
step three: grinding the product B, then putting the ground solid powder into a freeze drying box, and standing for 3-6 h at the low temperature of-10 to-30 ℃;
step four: and taking out the product, putting the product into a high-temperature tube furnace, rapidly heating to 700-800 ℃ at a heating rate of 10-30 ℃/min in an inert gas atmosphere, naturally cooling to room temperature after heating, and taking out to obtain a product C, namely the FeCoCuZnNi composite CNTs material.
Preferably, the nickel source is any one of analytically pure nickel sulfate, nickel nitrate, nickel chloride, nickel sulfamate, nickel bromide or nickel protoxide.
Preferably, the iron source is any one of ammonium ferrous sulfate, ferrous chloride, ammonium ferric oxalate and ferric citrate;
the cobalt source is any one of cobalt nitrate, cobalt sulfate or cobalt carbonate;
the copper source is any one of cuprous chloride, copper sulfate or copper nitrate;
the zinc source is any one of zinc sulfate heptahydrate, zinc sulfate monohydrate or zinc acetate.
Preferably, the carbon source is any one of urea, melamine or glucose.
Preferably, the high-speed centrifugation is carried out at a rotating speed of 1500-2500 r/min for 5-30 min.
Preferably, the inert atmosphere of the second step and the fourth step is a flowing argon or nitrogen atmosphere of 100 sccm.
Preferably, the grinding method in the third step is grinding for 20-30 min by using a mortar.
The invention also protects the FeCoCuZnNi composite CNTs material prepared by the preparation method.
Compared with the prior art, the invention has the following technical effects:
the invention controls the process conditions in the reaction process, and is matched with an alloy catalyst consisting of transition metals of iron, cobalt, copper, zinc and nickel to catalyze the growth of the carbon nano tube, the introduction of the transition metals provides the generation of defect sites, the increase of the defects of the carbon nano tube is realized, and the mutual bonding effect is generated between the transition metals and the exposed bond sites between the defects, so that the structure is changed, a uniform and very stable carbon tube structure with high graphitization is formed, more reaction sites are provided for the collapsed tube wall in the ion embedding process, and the prepared carbon nano tube has excellent electric conductivity, rich pore structure and good cycle performance;
the raw materials used in the invention are cheap and easily available, and the preparation method is simple.
Drawings
FIG. 1 is an XRD pattern of FeCoCuZnNi composite CNTs material of the invention;
FIG. 2 is a TEM image of FeCoCuZnNi composite CNTs material of the invention.
Detailed Description
The present invention will be explained in further detail with reference to examples.
Example 1
The method comprises the following steps: weighing ferrous sulfate, cobalt sulfate, copper nitrate, zinc acetate, nickel sulfate and urea according to the weight ratio of iron to cobalt to copper to zinc to nickel to carbon atom substances of 0.1:0.1:0.1:5:20, mixing, adding into a high-speed centrifugal dispersion tank, dispersing the materials in the high-speed centrifugal dispersion tank at the rotating speed of 1500r/min for 30min, and taking out to obtain a mixture A;
step two: placing the mixture A in a high-temperature tubular furnace, rapidly heating to 140 ℃ from room temperature at a heating rate of 15 ℃/min in a flowing argon atmosphere of 100sccm, preserving heat for 1h, naturally cooling to room temperature after heat preservation, and taking out to obtain a product B;
step three: grinding the product B for 20min by using a mortar, then putting the ground solid powder into a freeze drying box, and standing for 6h at the low temperature of-10 ℃;
step four: and taking out the product, putting the product into a high-temperature tubular furnace, rapidly heating the product to 700 ℃ at the heating rate of 10 ℃/min in the flowing argon atmosphere of 100sccm, naturally cooling the product to room temperature after heating, and taking out the product to obtain a product C, namely the FeCoCuZnNi composite CNTs material.
Example 2
The method comprises the following steps: weighing ferrous chloride, cobalt carbonate, copper nitrate, zinc sulfate monohydrate, nickel sulfate and urea according to the weight ratio of iron to cobalt to copper to zinc to nickel to carbon atom substances of 1:1:1:20:50, mixing, adding into a high-speed centrifugal dispersion tank, dispersing the materials in the high-speed centrifugal dispersion tank at the rotating speed of 2500r/min for 5min, and taking out to obtain a mixture A;
step two: placing the mixture A in a high-temperature tubular furnace, rapidly heating to 200 ℃ from room temperature at a heating rate of 30 ℃/min in a flowing argon atmosphere of 100sccm, preserving heat for 0.5h, naturally cooling to room temperature after heat preservation, and taking out to obtain a product B;
step three: grinding the product B for 25min by using a mortar, then putting the ground solid powder into a freeze drying box, and standing for 3h at the low temperature of-30 ℃;
step four: and taking out the product, putting the product into a high-temperature tubular furnace, rapidly heating to 800 ℃ at the heating rate of 30 ℃/min in the flowing argon atmosphere of 100sccm, naturally cooling to room temperature after heating, and taking out the product to obtain a product C, namely the FeCoCuZnNi composite CNTs material.
Example 3
The method comprises the following steps: weighing ammonium ferric oxalate, cobalt nitrate, copper nitrate, zinc sulfate heptahydrate, nickel sulfate and urea according to the weight ratio of iron to cobalt to copper to zinc to nickel to carbon atom substances of 0.3:0.3:0.3:10:30, mixing, adding into a high-speed centrifugal dispersion tank, dispersing the materials in the high-speed centrifugal dispersion tank at the rotating speed of 2000r/min for 20min, and taking out to obtain a mixture A;
step two: placing the mixture A in a high-temperature tubular furnace, rapidly heating to 180 ℃ from room temperature at a heating rate of 20 ℃/min in a flowing argon atmosphere of 100sccm, preserving heat for 0.8h, naturally cooling to room temperature after heat preservation, and taking out to obtain a product B;
step three: grinding the product B for 30min by using a mortar, then putting the ground solid powder into a freeze drying box, and standing for 5h at the low temperature of-20 ℃;
step four: and taking out the product, putting the product into a high-temperature tubular furnace, rapidly heating to 750 ℃ at the heating rate of 20 ℃/min in the flowing argon atmosphere of 100sccm, naturally cooling to room temperature after heating, and taking out the product to obtain a product C, namely the FeCoCuZnNi composite CNTs material.
Example 4
The method comprises the following steps: weighing ferric citrate, cobalt nitrate, copper nitrate, zinc acetate, nickel sulfate and urea according to the weight ratio of iron to cobalt to copper to zinc to nickel to carbon atom substances of 0.1:1:0.5:0.7:10:45, mixing, adding into a high-speed centrifugal dispersion tank, dispersing the materials in the high-speed centrifugal dispersion tank at the rotating speed of 2500r/min for 20min, and taking out to obtain a mixture A;
step two: placing the mixture A in a high-temperature tubular furnace, rapidly heating to 200 ℃ from room temperature at a heating rate of 25 ℃/min in a flowing argon atmosphere of 100sccm, preserving heat for 0.5h, naturally cooling to room temperature after heat preservation, and taking out to obtain a product B;
step three: grinding the product B for 20min by using a mortar, then putting the ground solid powder into a freeze drying box, and standing for 5h at the low temperature of-15 ℃;
step four: and taking out the product, putting the product into a high-temperature tubular furnace, rapidly heating to 750 ℃ at the heating rate of 20 ℃/min in the flowing argon atmosphere of 100sccm, naturally cooling to room temperature after heating, and taking out the product to obtain a product C, namely the FeCoCuZnNi composite CNTs material.
When the FeCoCuZnNi composite CNTs material prepared in example 1 is subjected to X-ray diffraction analysis, as shown in FIG. 1, a carbon peak at 26.25 degrees 2 theta, 44.35 and 51.7 degrees 2 theta, which corresponds to standard card PDF #70-1849, can be obviously seen from FIG. 1, and the peak intensity is high and sharp, and the crystallinity is good.
The morphology of a transmission electron microscope of the FeCoCuZnNi composite CNTs material synthesized in the embodiment 1 is shown in FIG. 2, the formed carbon nanotubes have uniform size, and in FIG. 2, it can be seen that the FeCoCuZnNi composite CNTs material has a hollow tubular structure with a complete morphology and the size of about 200nm, and it can be seen from the figure that a large number of folds exist on the surface of the carbon nanotubes due to the existence of the alloy, so that the specific surface area is increased, and the carbon nanotubes have rich active sites.
The foregoing is a further detailed description of the present invention and it should not be considered that the embodiments of the present invention are limited thereto, and that the iron source, the cobalt source, the copper source, the nickel source, the zinc source and the carbon source may be combined with other substances provided for the technical solution or in other ratios within the technical solution, and that a person skilled in the art to which the present invention pertains may make several simple deductions or substitutions without departing from the concept of the present invention, and all should be considered as falling within the scope of protection of the present invention as determined by the claims submitted.
Claims (8)
1. A preparation method of FeCoCuZnNi composite CNTs material is characterized by comprising the following steps:
the method comprises the following steps: weighing an iron source, a cobalt source, a copper source, a zinc source, a nickel source and a carbon source according to the weight ratio of atomic substances (0.1-1) to (5-20) to (20-50), mixing, and then centrifuging at a high speed to obtain a mixture A;
step two: placing the mixture A in a high-temperature tube furnace, rapidly heating the mixture A to 140-200 ℃ from room temperature at a heating rate of 15-30 ℃/min in an inert gas atmosphere, preserving heat for 0.5-1 h, naturally cooling to room temperature after heat preservation is finished, and taking out to obtain a product B;
step three: grinding the product B, then putting the ground solid powder into a freeze drying box, and standing for 3-6 h at the low temperature of-10 to-30 ℃;
step four: and taking out the product, putting the product into a high-temperature tube furnace, rapidly heating the product to 700-800 ℃ from room temperature at a heating rate of 10-30 ℃/min in an inert gas atmosphere, naturally cooling the product to room temperature after heating, and taking out the product to obtain a product C, namely the FeCoCuZnNi composite CNTs material.
2. The method for preparing FeCoCuZnNi composite CNTs material according to claim 1, wherein the nickel source is any one of analytically pure nickel sulfate, nickel nitrate, nickel chloride, nickel sulfamate, nickel bromide or nickel oxyhydroxide.
3. The method for preparing FeCoCuZnNi composite CNTs material according to claim 1, wherein the iron source is any one of ferrous ammonium sulfate, ferrous chloride, ammonium ferric oxalate and ferric citrate;
the cobalt source is any one of cobalt nitrate, cobalt sulfate or cobalt carbonate;
the copper source is any one of cuprous chloride, copper sulfate or copper nitrate;
the zinc source is any one of zinc sulfate heptahydrate, zinc sulfate monohydrate or zinc acetate.
4. The method for preparing FeCoCuZnNi composite CNTs material according to claim 1, wherein the carbon source is any one of urea, melamine or glucose.
5. The method for preparing FeCoCuZnNi composite CNTs material according to claim 1, wherein the high speed centrifugation is carried out at a rotation speed of 1500-2500 r/min for 5-30 min.
6. The method for preparing FeCoCuZnNi composite CNTs material according to claim 1, wherein the inert atmosphere in the second and fourth steps is flowing argon or nitrogen atmosphere of 100 sccm.
7. The preparation method of the FeCoCuZnNi composite CNTs material as claimed in claim 1, wherein the grinding method in the third step is grinding for 20-30 min by using a mortar.
8. FeCoCuZnNi composite CNTs material prepared by the preparation method according to any one of claims 1 to 7.
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