CN113611880A - Carbon nanotube-loaded transition metal composite material and preparation method and application thereof - Google Patents
Carbon nanotube-loaded transition metal composite material and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 38
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 36
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 29
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000002905 metal composite material Substances 0.000 title claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 16
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002738 chelating agent Substances 0.000 claims abstract description 12
- 239000002131 composite material Substances 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 32
- 150000003623 transition metal compounds Chemical class 0.000 claims description 20
- 229910052742 iron Inorganic materials 0.000 claims description 15
- 239000011701 zinc Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical group OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000007774 positive electrode material Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 11
- 239000002105 nanoparticle Substances 0.000 abstract description 8
- 238000003763 carbonization Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 229910021524 transition metal nanoparticle Inorganic materials 0.000 abstract description 5
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 31
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 12
- 239000000843 powder Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 239000002923 metal particle Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000010757 Reduction Activity Effects 0.000 description 3
- 230000009920 chelation Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000002082 metal nanoparticle Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000000527 sonication Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910003321 CoFe Inorganic materials 0.000 description 1
- 229910002546 FeCo Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910007613 Zn—MnO2 Inorganic materials 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910021386 carbon form Inorganic materials 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- -1 transition metal salt Chemical class 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
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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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Inert Electrodes (AREA)
Abstract
The invention relates to the technical field of battery materials, in particular to a carbon nano tube loaded transition metal composite material and a preparation method and application thereof. The invention discloses a preparation method of a carbon nano tube loaded transition metal composite material, which adopts a chelating agent to enable transition metal atoms to form smaller nano particles to increase the active sites of the nano particles, and uses nitrogen-doped carbon formed by melamine carbonization as a template, and the synthesized transition metal nano particles are loaded on the nitrogen-doped carbon template. Because the catalyst of the transition metal nano particles forms the carbon nano tubes in situ during the carbonization of the melamine, the carbon nano tubes do not need to be additionally added, the preparation cost of the composite material is greatly reduced, and the preparation method is simple.
Description
Technical Field
The invention relates to the technical field of battery materials, in particular to a carbon nano tube loaded transition metal composite material and a preparation method and application thereof.
Background
The metal-air battery consists of a metal anode, an air electrode and electrolyte. The metal-air battery generates an electric current by oxidation-reduction reaction of metal and air. The metal-air cell device has an open cell structure that allows for continuity and freedom from an external source (air)To the cathode material in a limited manner. This feature is similar to a fuel cell, and the fuel is metal. With conventional Zn-MnO2Compared with batteries, rechargeable lead-acid batteries, nickel-metal hydride batteries and lithium ion batteries, metal-air batteries have higher theoretical energy density. These high energy cells are due to the fact that cathode oxygen is not stored in the cell and the anode metal has high valence electrons. Meanwhile, the device has the advantages of high energy conversion efficiency, environmental friendliness, quick start and stop and the like.
The aluminum-air battery has the advantages of low operation temperature, low cost, high energy density and the like, and is energy storage equipment with wide application prospect. The oxygen reduction catalyst is used as an important component of the aluminum-air battery, and has the problems of poor electrochemical polarization, poor oxygen reduction kinetics and the like, so that the application development of the aluminum-air battery is greatly limited. However, the catalyst platinum carbon (Pt/C) commonly used in the air electrode has high catalytic activity but is too expensive, and cannot be applied on a large scale. Therefore, it is of great significance to develop a transition metal catalyst with high performance, long stability and low cost for an aluminum-air battery.
Disclosure of Invention
In view of the above, the invention provides a carbon nanotube-loaded transition metal composite material, and a preparation method and an application thereof.
The specific technical scheme is as follows:
the invention provides a preparation method of a carbon nano tube loaded transition metal composite material, which comprises the following steps:
adding a compound containing transition metal, a chelating agent and melamine into an organic solvent, heating, grinding the remainder after the organic solvent is evaporated, and calcining under nitrogen or inert gas to obtain the transition metal loaded carbon nanotube composite material.
The invention adopts chelating agent to enable transition metal atoms to form smaller nano particles to increase the active sites of the nano particles, nitrogen-doped carbon formed by carbonizing melamine is taken as a template, and the synthesized transition metal nano particles are loaded on the nitrogen-doped carbon template. According to the invention, because small molecular hydrocarbon can be formed during high-temperature carbonization of melamine, the hydrocarbon can be attached to the surface of metal nano particles and can be fused into metal, because the solubility of carbon in metal is very low, carbon can be separated out again when the metal is saturated, the carbon separated out again can form different carbon forms according to different components of the metal particles, and when the solubility is too low, a layer of graphite can be directly formed around the metal particles to wrap the metal particles, and the reaction stops. In addition, the carbon nano tube is not additionally added, so that the preparation cost of the composite material is greatly reduced.
In the invention, the adding of the transition metal-containing compound, the chelating agent and the melamine into the organic solvent specifically comprises the following steps: respectively dissolving a transition metal compound, a chelating agent and melamine in an organic solvent, mixing the transition metal compound solution with the chelating agent solvent, and finally mixing with the melamine solution.
The transition metal in the transition metal compound comprises one or more of iron, cobalt and zinc;
the transition metal compound is preferably a transition metal salt;
the chelating agent is EDTA;
the mass ratio of the transition metal compound to the chelating agent to the melamine is (0.01-0.5): (0.1-5): (1-20), preferably (0.05-0.25): (0.1-1): (5-15), more preferably (0.1-0.15): 0.4: 10;
when the transition metal in the transition metal compound is iron, zinc and cobalt, the mass ratio of the iron to the zinc to the cobalt in the transition metal compound is (1-5): (1-2): (1-5), preferably 1: 1: 1;
when the transition metal in the transition metal compound is cobalt and iron, the mass ratio of the cobalt to the iron in the transition metal compound is (1-5): (1-2), preferably 1: 1;
when the transition metal in the transition metal compound is iron and zinc, the mass ratio of the iron to the zinc in the transition metal compound is (1-5): (1-2), preferably 1: 1.
the organic solvent is one or more than two of ethanol, deionized water, methanol and acetone, and ethanol is preferred;
the heating is preferably carried out under an oil bath; the temperature of the oil bath is 40-100 ℃, and preferably 60 ℃;
the purpose of grinding the remainder is to grind the remainder into powder so that the remainder is better and uniformly mixed with subsequent products and is convenient for subsequent treatment, and the grain size of the remainder grinding is not particularly limited;
the calcining temperature is 600-1100 ℃, the time is 0.5-3 h, and the temperature is preferably kept at 900 ℃ for 1 h.
The invention also provides a carbon nano tube loaded transition metal composite material prepared by the preparation method, which comprises the following steps: carbon nanotubes and a transition metal supported on the carbon nanotubes.
The invention also provides application of the carbon nano tube loaded transition metal composite material in a metal-air battery.
The invention also provides a metal-air battery anode material which comprises the carbon nano tube loaded transition metal composite material.
The invention also provides a metal-air battery anode which comprises the carbon nano tube loaded transition metal composite material.
The invention also provides a metal-air battery which comprises the positive electrode and the negative electrode of the metal-air battery.
According to the technical scheme, the invention has the following advantages:
the invention provides a preparation method of a carbon nano tube loaded transition metal composite material, which adopts a chelating agent to enable transition metal atoms to form smaller nano particles to increase the active sites of the nano particles, and uses nitrogen-doped carbon formed by melamine carbonization as a template, and the synthesized transition metal nano particles are loaded on the nitrogen-doped carbon template. Because the catalyst of the transition metal nano particles forms the carbon nano tubes in situ during the carbonization of the melamine, the carbon nano tubes do not need to be additionally added, and the preparation cost of the composite material is greatly reduced. The preparation method has low preparation cost and is simple.
In addition, the carbon nanotube-loaded transition metal composite material prepared by the invention has excellent oxygen reduction electrocatalytic activity, can surpass a commercial Pt/C catalyst in an alkaline electrolyte, and has a half-wave potential of 0.91Vvs. And exhibits a higher power density, 100mA cm, than commercial Pt/C-2Long-term discharge performance and step discharge performance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without inventive exercise.
FIG. 1 is a schematic diagram of the synthesis process of FeCoNP @ N-CNT prepared in example 1 of the present invention;
FIG. 2 is an XRD pattern of FeCoNP @ N-CNT, CoNP @ N-CNT and FeNP @ N-CNT prepared in examples 1 to 3 of the present invention;
FIG. 3 is an SEM image of FeCoNP @ N-CNT prepared in example 1 of the present invention;
FIG. 4 is an SEM image of CoNP @ N-CNT made in example 2 of the present invention;
FIG. 5 is an SEM image of FeNP @ N-CNT obtained in example 3 of the present invention;
FIG. 6 is a graph showing the oxygen reduction activity of FeCoNP @ N-CNT, CoNP @ N-CNT, and FeNP @ N-CNT prepared in examples 1 to 3 of the present invention and commercial Pt/C;
fig. 7 is a schematic diagram showing the results of the metal-air battery provided in example 5 of the present invention;
fig. 8 and 9 are graphs showing power test results of the metal-air battery provided in example 5 of the present invention;
FIG. 10 shows a 100mA cm metal-air battery provided in example 5 of the present invention-2A constant current discharge test result graph;
fig. 11 is a graph illustrating a step discharge test result of the metal-air battery provided in embodiment 5 of the present invention.
Detailed Description
In order to make the objects, features and advantages of the present invention more obvious and understandable, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it should be apparent that the embodiments described below are only a part of the embodiments of the present invention, and not all 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.
Example 1
This example is a preparation of a carbon nanotube supported transition metal composite FeCoNP @ N-CNT, as shown in fig. 1, and the specific preparation steps are as follows:
solution A: 50mg of cobalt nitrate, 50mg of iron nitrate and 50mg of zinc nitrate were dissolved in 30ml of ethanol, and the mixture was magnetically stirred for 10 minutes to completely dissolve the cobalt nitrate, the iron nitrate and the zinc nitrate.
Solution B: 0.4g of EDTA was dissolved in 30ml of ethanol, and the mixture was stirred for 30 minutes after 10 minutes of sonication until complete dissolution.
Solution C: 10g of melamine were dissolved in 30ml of ethanol and stirred for 10 minutes until completely dissolved.
The solution A was added dropwise to the solution B and then sonicated for 10 minutes, followed by stirring for 30 minutes to allow for sufficient chelation. After dropwise addition of the solution C to the mixed solution of the solution A and the solution B, heating was carried out at a temperature of 60 ℃ in an oil bath (rotation speed 400 rpm). After the ethanol is completely evaporated to dryness, light yellow powder is obtained, the powder is ground for 30 minutes and then is put into a tubular furnace filled with inert gas (nitrogen) for calcination, the temperature rise speed is 5 ℃ per minute, the heat preservation temperature is 900 ℃, and the heat preservation time is 1 hour. And grinding the obtained black powder for 30 minutes after the heat treatment is finished to obtain the final FeCoNP @ N-CNT material.
Example 2
The embodiment is a preparation method of a carbon nanotube loaded transition metal composite material CoNP @ N-CNT, and the preparation method specifically comprises the following steps:
solution A: 50mg of cobalt nitrate and 50mg of zinc nitrate were dissolved in 30ml of ethanol, and the mixture was magnetically stirred for 10 minutes to completely dissolve the cobalt nitrate and the zinc nitrate.
Solution B: 0.4g of EDTA was dissolved in 30ml of ethanol, and the mixture was stirred for 30 minutes after 10 minutes of sonication until complete dissolution.
Solution C: 10g of melamine were dissolved in 30ml of ethanol and stirred for 10 minutes until completely dissolved.
The solution A was added dropwise to the solution B and then sonicated for 10 minutes, followed by stirring for 30 minutes to allow for sufficient chelation. After dropwise addition of the solution C to the mixed solution of the solution A and the solution B, heating was carried out at a temperature of 60 ℃ in an oil bath (rotation speed 400 rpm). After the ethanol is completely evaporated to dryness, light yellow powder is obtained, the powder is ground for 30 minutes and then is put into a tubular furnace filled with inert gas (nitrogen) for calcination, the temperature rise speed is 5 ℃ per minute, the heat preservation temperature is 900 ℃, and the heat preservation time is 1 hour. After the heat treatment was completed, the resulting black powder was ground for 30 minutes to obtain the final CoNP @ N-CNT material.
Example 3
The embodiment is a preparation method of a carbon nanotube loaded transition metal composite material FeNP @ N-CNT, and the preparation method specifically comprises the following steps:
solution A: 50mg of ferric nitrate and 50mg of zinc nitrate were dissolved in 30ml of ethanol, and the mixture was magnetically stirred for 10 minutes to completely dissolve the ferric nitrate and the zinc nitrate.
Solution B: 0.4g of EDTA was dissolved in 30ml of ethanol, and the mixture was stirred for 30 minutes after 10 minutes of sonication until complete dissolution.
Solution C: 10g of melamine were dissolved in 30ml of ethanol and stirred for 10 minutes until completely dissolved.
The solution A was added dropwise to the solution B and then sonicated for 10 minutes, followed by stirring for 30 minutes to allow for sufficient chelation. After dropwise addition of the solution C to the mixed solution of the solution A and the solution B, heating was carried out at a temperature of 60 ℃ in an oil bath (rotation speed 400 rpm). After the ethanol is completely evaporated to dryness, light yellow powder is obtained, the powder is ground for 30 minutes and then is put into a tubular furnace filled with inert gas (nitrogen) for calcination, the temperature rise speed is 5 ℃ per minute, the heat preservation temperature is 900 ℃, and the heat preservation time is 1 hour. And grinding the obtained black powder for 30 minutes after the heat treatment is finished to obtain the final FeNP @ N-CNT material.
Example 4
1. XRD characterization was performed on FeCoNP @ N-CNT, CoNP @ N-CNT, and FeNP @ N-CNT obtained in examples 1 to 3, and the results are shown in FIG. 2.
As shown in FIG. 2, FeCoNP @ N-CNT, CoNP @ N-CNT, and FeNP @ N-CNT were successfully prepared in examples 1 to 3. The main phase of FeCoNP @ N-CNT is Co and Fe to form alloy nano-particle Co0.7Fe0.3(ii) a The main phase of CoNP @ N-CNT is Co metal nanoparticles; the main phase of the FeNP @ N-CNT is Fe metal nanoparticles.
2. SEM and TEM characterization of FeCoNP @ N-CNT prepared in example 1 are shown in FIG. 3.
As shown in FIG. 3, FeCo @ N-CNT carbon tubes have uniform and dense diameters, and the diameter of the metal particles compounded at the end of the carbon tube is about 10 nm. Embodying Co0.7Fe0.3The nanoparticles have excellent catalytic properties for forming carbon nanotubes.
3. SEM characterization of the CoNP @ N-CNT prepared in example 2 is shown in FIG. 4.
As shown in fig. 4, the cenp @ N-CNT carbon tubes have a lower density and a shorter length.
4. SEM characterization of the FeNP @ N-CNT prepared in example 3 is shown in FIG. 5.
As shown in fig. 5, the FeNP @ N-CNT carbon tubes have a lower density and a shorter length.
Example 5
FeCoNP @ N-CNT, CoNP @ N-CNT, FeNP @ N-CNT and commercial Pt/C prepared in examples 1-3 were tested for oxygen reduction activity, and the specific preparation steps were as follows:
4mg of each of the samples prepared in examples 1 to 3 was weighed into a sample bottle, and subjected to ultrasonication for 30 minutes after adding 0.5ml of ethanol, 0.5ml of water, and 40. mu.l of Nafion. After the ultrasonic treatment, 12.4 mu L of solution is dripped onto a glassy carbon electrode by using a pipette gun, and the water and alcohol are dried by using an infrared lamp (catalyst loading amount: 0.4 mg/cm)2). Taking a glassy carbon electrode as a working electrode, Ag/AgCl as a reference electrode, a platinum wire as a counter electrode and 0.1M KOH solution as electrolyte, carrying out a linear voltammetry test at a rotation speed of 1600 rpm, wherein a scanning interval is 0.2-1.0V (vs. RHE), and a test result is shown in FIG. 6。
As shown in FIG. 6, the oxygen reduction activity of FeCoNP @ N-CNT, CoNP @ N-CNT and FeNP @ N-CNT catalysts are all due to commercial Pt/C catalysts, wherein the half-wave potential of FeCoNP @ N-CNT reaches 0.91V (vs.
Example 5
The metal-air cell was assembled as follows: the solution preparation process was identical to the above process, 6.5 × 2cm of hydrophilic-hydrophobic carbon cloth was cut, 562.5 μ L of the above solution was dropped on the hydrophilic side uniformly to a range of 1.5 × 1.5cm (carbon cloth catalyst loading: 1 mg/cm)2) And drying to obtain the air electrode. Assembling into air battery with special mold, taking pure aluminum as cathode, coating with 1mg/cm2Carbon cloth of CoFe (Zn) (NP) @ NC, CoNP @ N-CNT, FeNP @ N-CNT and Pt/C is taken as a positive electrode, and a proper amount of 6M KOH is added to be taken as electrolyte. The metal-air cell mold is shown in fig. 7.
Cells assembled as described above were power tested for FeCoNP @ N-CNT, CoNP @ N-CNT, FeNP @ N-CNT, and Pt/C. The test results are shown in fig. 8 and 9.
As shown in FIGS. 8 and 9, the peak power of FeCoNP @ N-CNT in the three prepared catalysts was up to 255.67mW cm-2Compared with commercial Pt/C193.73 mW cm-2Much higher.
Cells assembled as described above were subjected to 100mA cm for FeCoNP @ N-CNT and Pt/C-2And (5) constant current discharge testing. The test results obtained are shown in FIG. 10.
As shown in FIG. 10, FeCoNP @ N-CNT discharges longer time, has better durability and higher discharge voltage than Pt/C.
The cells assembled as described above were subjected to a step discharge test with FeCoNP @ N-CNT and Pt/C. The test results obtained are shown in FIG. 11.
As shown in FIG. 11, FeCoNP @ N-CNT gives higher discharge voltage at various current densities than Pt/C.
The above-mentioned embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of a carbon nanotube-loaded transition metal composite material is characterized by comprising the following steps:
adding a transition metal compound, a chelating agent and melamine into an organic solvent, heating, grinding the remainder after the organic solvent is evaporated, and calcining under nitrogen or inert gas to obtain the transition metal loaded carbon nanotube composite material.
2. The method according to claim 1, wherein the transition metal in the transition metal compound includes one or more of iron, cobalt, and zinc.
3. The method according to claim 1, wherein the heating temperature is 40 to 100 ℃.
4. The preparation method according to claim 1, wherein the calcining temperature is 600-1100 ℃ and the calcining time is 0.5-3 h.
5. The production method according to claim 1, wherein the mass ratio of the transition metal compound, the chelating agent, and the melamine is (0.01 to 0.5): (0.1-5): (1-20).
6. The method of claim 1, wherein the chelating agent is EDTA.
7. The preparation method according to claim 1, wherein when the transition metal in the transition metal compound is iron, zinc and cobalt, the mass ratio of iron, zinc and cobalt in the transition metal compound is (1-5): (1-2): (1-5);
when the transition metal in the transition metal compound is cobalt and iron, the mass ratio of the cobalt to the iron in the transition metal compound is (1-5): (1-2);
when the transition metal in the transition metal compound is iron and zinc, the mass ratio of the iron to the zinc in the transition metal compound is (1-5): (1-2).
8. The carbon nanotube-supported transition metal composite material produced by the production method according to any one of claims 1 to 7, comprising: carbon nanotubes and a transition metal supported on the carbon nanotubes.
9. Use of the carbon nanotube-supported transition metal composite of claim 8 in a metal-air battery.
10. A metal-air battery positive electrode material, characterized by comprising: the carbon nanotube-supported transition metal composite of claim 8.
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