CN110787819A - Cobalt diselenide/nitrogen-doped carbon nano material composite electrode catalytic material and preparation method and application thereof - Google Patents
Cobalt diselenide/nitrogen-doped carbon nano material composite electrode catalytic 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 182
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 141
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 52
- GAIMSHOTKWOMOB-UHFFFAOYSA-N [Se]=[Co]=[Se] Chemical compound [Se]=[Co]=[Se] GAIMSHOTKWOMOB-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 239000000463 material Substances 0.000 title claims abstract description 42
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 45
- 239000002135 nanosheet Substances 0.000 claims abstract description 44
- 239000004744 fabric Substances 0.000 claims abstract description 43
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 18
- 239000012921 cobalt-based metal-organic framework Substances 0.000 claims abstract description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 238000011065 in-situ storage Methods 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 239000012917 MOF crystal Substances 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000004146 energy storage Methods 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 238000001354 calcination Methods 0.000 description 11
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 239000012621 metal-organic framework Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 238000003760 magnetic stirring Methods 0.000 description 5
- 239000010405 anode material Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 3
- 239000013354 porous framework Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 150000003346 selenoethers Chemical class 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 238000009827 uniform distribution Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- QVYIMIJFGKEJDW-UHFFFAOYSA-N cobalt(ii) selenide Chemical compound [Se]=[Co] QVYIMIJFGKEJDW-UHFFFAOYSA-N 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
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- 239000007772 electrode material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
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- 238000012377 drug delivery Methods 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01J35/33—
-
- B01J35/60—
-
- 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
- H01M4/90—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
- H01M4/9075—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
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the technical field of composite materials, and provides a cobalt diselenide/nitrogen-doped carbon nano material composite electrode catalytic material and a preparation method and application thereof, aiming at solving the problems of high price and low catalytic activity of the electrode catalytic material of the existing zinc-air battery, wherein the preparation method comprises the following steps: (1) growing Co-MOF on the carbon cloth subjected to hydrophilization treatment; (2) growing a nitrogen-doped carbon nano material by a CVD (chemical vapor deposition) method to obtain a Co/nitrogen-doped carbon nano material; the nitrogen-doped carbon nano material is a combination of a nitrogen-doped carbon nano tube and a nitrogen-doped carbon nano sheet; (3) selenizing to prepare the cobalt diselenide/nitrogen-doped carbon nano material composite electrode catalytic material. The composite material disclosed by the invention reserves the structural integrity of a cobalt diselenide porous frame/carbon nanosheet array obtained by taking a triangular flaky MOF crystal as a template, has the excellent performances of a carbon nanotube and the cobalt diselenide porous frame, and has a wide application prospect in the fields of adsorption, sensing, energy storage, catalysis and the like.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a cobalt diselenide/nitrogen-doped carbon nano material composite electrode catalytic material, and a preparation method and application thereof.
Background
Nowadays, as the global energy consumption and demand are drastically increased due to the continuous growth of economy and population, the development and utilization of new energy sources are urgently needed in order to reduce the gradual depletion of fossil fuels and the accompanying climate problems. The zinc-air battery is used as a novel energy conversion device, has the advantages of high energy density, environmental friendliness, long service life, high energy conversion efficiency, low price and the like, and is widely concerned by people.
Among them, the electrode catalytic material of the zinc-air battery is a key factor determining the performance and cost of the battery. Currently, the most commonly used and effective catalyst is a noble metal catalyst, but its wide application in industry is limited due to its high price and small storage amount. Therefore, it is very important to develop an electrode material with low cost and high catalytic activity.
Metal-organic framework compounds (MOFs), are formed by coordination of organic ligands with metal ions/clusters through complexation. MOF materials have great potential in gas storage, chemical separation, selective catalysis, and drug delivery. The intrinsically porous structure of MOFs facilitates electrolyte penetration and ion transport, and the use of MOFs as MOF-derived materials obtained from sacrificial templates is more promising as electrode materials, since they mostly inherit not only the porous structure of the MOF precursor, but also exhibit good electrical conductivity provided by carbon. Therefore, the MOF is used as a precursor, and the obtained porous selenide/carbon composite material has a good application prospect in clean energy.
The Chinese patent literature discloses a cobalt selenide/carbon sodium ion battery composite cathode material and a preparation method and application thereof, wherein the publication number is CN105789584A, the cobalt selenide/carbon composite material prepared by the invention has good dispersibility and a uniform nano rod-shaped structure, and has higher charge-discharge specific capacity, good rate capability and cycling stability as a sodium ion battery cathode material, but the composite cathode material has lower specific surface area and poor bending resistance, and cannot be applied to flexible batteries.
Disclosure of Invention
The invention provides a preparation method of a cobalt diselenide/nitrogen-doped carbon nano material composite electrode catalytic material, aiming at overcoming the problems of high price and low catalytic activity of the electrode catalytic material of the existing zinc-air battery.
The invention also provides the cobalt diselenide/nitrogen-doped carbon nano material composite electrode catalytic material prepared by the method, the structural integrity of a cobalt diselenide porous frame/carbon nano sheet array obtained by taking the triangular flaky MOF crystal as a template is reserved, the excellent performances of the carbon nano tube and the cobalt diselenide porous frame are combined, and compared with the traditional zinc-air battery electrode catalytic material, the cobalt diselenide/nitrogen-doped carbon nano material composite electrode catalytic material has the advantages of high catalytic activity, low price, excellent conductivity, good flexibility and the like.
The invention also provides application of the cobalt diselenide/nitrogen-doped carbon nano material composite electrode catalytic material in a zinc-air battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a cobalt diselenide/nitrogen-doped carbon nano material composite electrode catalytic material comprises the following steps:
(1) growing Co-MOF in situ on the carbon cloth subjected to hydrophilization treatment by a hydrothermal method;
(2) growing a nitrogen-doped carbon nano material on the carbon cloth treated in the step (1) by a CVD (chemical vapor deposition) method to obtain a Co/nitrogen-doped carbon nano material; the nitrogen-doped carbon nano material is a combination of a nitrogen-doped carbon nano tube and a nitrogen-doped carbon nano sheet;
(3) and (3) selenizing the Co/nitrogen-doped carbon nano material grown on the surface of the carbon cloth in the step (2) to obtain the cobalt diselenide/nitrogen-doped carbon nano material composite electrode catalytic material.
According to the invention, the Co-MOF sheet is grown on the carbon cloth subjected to hydrophilization treatment by a hydrothermal method, and the sheet-shaped array structure cobalt diselenide porous frame/nitrogen-doped carbon nano material composite electrode catalytic material is prepared after two-step calcination.
Preferably, the hydrophilization treatment method of the carbon cloth comprises the following steps: the carbon cloth is sequentially soaked in acetone (99.5%), 10% hydrochloric acid and ethanol (99.7%), then washed to be neutral by deionized water, dried for 24 hours in vacuum at 60 ℃ and finally subjected to plasma hydrophilization for later use.
Preferably, in the step (2), the CVD method specifically includes: firstly introducing nitrogen to exhaust air, heating to 300-600 ℃ at the speed of 3-5 ℃/min, introducing ethanol and hydrogen to calcine for 0.1-1 h, then keeping for 1-3 h under the nitrogen atmosphere, and finally naturally cooling to obtain the Co/nitrogen-doped carbon nanomaterial.
Preferably, in step (3), the selenization process includes: selenium powder is added into the Co/nitrogen-doped carbon nano material, and the Co/nitrogen-doped carbon nano material is calcined for 1-20 hours at the temperature of 300-600 ℃.
Preferably, the mass ratio of the selenium powder to the Co/nitrogen-doped carbon nano material is 1: (8-10).
Preferably, in the step (2), the length of the nitrogen-doped carbon nanotube is 50 to 200 nm.
Preferably, in the step (2), the nitrogen-doped carbon nanosheet is of a triangular structure, and the side length of the nitrogen-doped carbon nanosheet is controlled to be 2-4 μm.
Preferably, in step (1), the Co-MOF has a two-dimensional triangular structure.
The cobalt diselenide porous frame/nitrogen-doped carbon nano material composite electrode catalytic material uniformly grows on the surface of carbon cloth, specifically, a two-dimensional triangular Co-MOF nanosheet array uniformly grows on the surface of the carbon cloth, then a nitrogen-doped carbon nanosheet and a nitrogen-doped carbon nano tube grow through a CVD (chemical vapor deposition) method, and the obtained Co/nitrogen-doped carbon nano material is subjected to selenylation treatment to obtain the cobalt diselenide/nitrogen-doped carbon nano material composite electrode catalytic material. The material has a porous structure, the integrity of the triangular structure of the MOF sheet is kept in the synthesis process, the material has the excellent performances of a carbon nano tube and a cobalt diselenide porous frame, the specific surface area of the array-shaped triangular two-dimensional nano sheet and the one-dimensional carbon tube structure is increased, and more active sites are exposed in the two-dimensional porous structure, so that the material is beneficial to electrocatalysis reaction. In addition, the composite material has a multi-level pore structure, specifically comprises micropores of the two-dimensional MOF, open pores among triangular carbon nanosheets in the array and macropores of the carbon cloth substrate, and is favorable for infiltration of electrolyte and separation of gas. The material can simultaneously play the advantages of the carbon nano tube and the porous cobalt diselenide in the fields of adsorption, sensing, energy storage, catalysis and the like, and the flaky array structure cobalt diselenide porous frame/nitrogen-doped carbon nano tube/carbon nano sheet composite material grows on carbon cloth and has certain flexibility. Therefore, the method has good application prospect in flexible electronic devices.
Preferably, the CVD method is specifically: firstly introducing nitrogen to exhaust air, heating to 300-600 ℃ at the speed of 5 ℃/min, introducing ethanol and hydrogen to calcine for 0.1-1 h, then keeping for 1-3 h under the nitrogen atmosphere, and finally naturally cooling to obtain the Co/nitrogen-doped carbon nanomaterial.
Preferably, the selenization treatment method comprises the following steps: selenium powder is added into the Co/nitrogen-doped carbon nano material, and the Co/nitrogen-doped carbon nano material is calcined for 1-20 hours at the temperature of 300-600 ℃.
Preferably, the mass ratio of the selenium powder to the Co/nitrogen-doped carbon nano material is 1: (8-10).
The composite electrode catalytic material grows on the surface of carbon cloth subjected to hydrophilization treatment, and is a multistage pore structure compounded by cobalt diselenide with a two-dimensional triangular structure, nitrogen-doped carbon nanotubes growing on the surface of the cobalt diselenide and nitrogen-doped nanosheets.
The cobalt diselenide/nitrogen-doped carbon nano material composite electrode catalytic material prepared by any one of the methods is applied to a zinc-air battery.
Therefore, the invention has the following beneficial effects:
(1) the mass production or the industrial production can be realized;
(2) the preparation method has mild conditions, simple operation, controllable structure and uniform component distribution;
(3) the composite electrode catalytic material reserves the structural integrity of a cobalt diselenide porous framework/carbon nanosheet array obtained by taking triangular flaky MOF crystals as templates, and has the excellent performances of carbon nanotubes and the cobalt diselenide porous framework.
Drawings
FIG. 1 is an SEM and TEM image of the product obtained in example 1: Co-MOF (1a), Co/nitrogen-doped carbon nano tube/nitrogen-doped carbon nano sheet (1b), and cobalt diselenide/nitrogen-doped carbon nano tube/nitrogen-doped carbon nano sheet composite electrode catalytic material (1c, 1e, 1d, 1 f).
Fig. 2 is a cycle performance diagram of a zinc-air battery prepared by using the cobalt diselenide/nitrogen-doped carbon nanotube/nitrogen-doped carbon nanosheet prepared in example 1 as a zinc-air battery composite electrode catalytic material.
Fig. 3 is a performance display diagram of a flexible zinc-air battery prepared by using the cobalt diselenide/nitrogen-doped carbon nanotube/nitrogen-doped carbon nanosheet prepared in example 1 as a zinc-air battery composite electrode catalytic material.
Detailed Description
The technical solution of the present invention is further specifically described below by way of specific examples.
In the present invention, all the equipment and materials are commercially available or commonly used in the art, and the methods in the following examples are conventional in the art unless otherwise specified.
Example 1
(1) Sequentially soaking carbon cloth in acetone (99.5%), 10% hydrochloric acid and ethanol (99.7%), washing with deionized water to be neutral, vacuum-drying at 60 ℃ for 24h, and performing plasma hydrophilization treatment to obtain the hydrophilized carbon cloth for later use; 40mL of an aqueous solution containing 1.3g of dimethylimidazole was added to 40mL of an aqueous solution containing 0.5821g of cobalt nitrate hexahydrate at room temperature, and the mixture was mixed uniformly with magnetic stirring, added to the above carbon cloth and reacted at room temperature for 4 hours. After the reaction is finished, the mixture is washed for 3 times by deionized water. After the obtained product is dried in vacuum at 60 ℃ for 24 hours, growing Co-MOF in situ on carbon cloth;
(2) growing nitrogen-doped carbon nano tubes/nitrogen-doped carbon nano sheets on the carbon cloth treated in the step (1) by a CVD (chemical vapor deposition) method, introducing nitrogen, heating to 500 ℃ at the speed of 3 ℃/min, introducing hydrogen and ethanol, calcining for 10 minutes, introducing nitrogen, keeping at 500 ℃ for 2 hours, and naturally cooling to room temperature under the protection of nitrogen to obtain Co/nitrogen-doped carbon nano tubes/nitrogen-doped carbon nano sheets with an array structure;
(3) and (3) adding 0.6g of selenium powder into the Co/nitrogen-doped carbon nanomaterial growing on the surface of the carbon cloth in the step (2), introducing hydrogen, heating to 300 ℃ at the rate of 5 ℃ per minute, calcining for 6 hours, and finally naturally cooling to obtain the cobalt diselenide porous frame/nitrogen-doped carbon nanotube/nitrogen-doped carbon nanomaterial.
The samples in this example were selected for characterization and analysis, with the following test results:
FIG. 1(a) is an SEM image of the two-dimensional Co-MOF obtained in example 1, and it can be seen from FIG. 1a that the obtained two-dimensional Co-MOF crystals have a triangular plate shape and a transverse dimension of 2 μm. As can be seen from the inset, the carbon cloth was uniformly covered with the triangular flake Co-MOF. Fig. 1(b) is the surface morphology of the Co/n-doped carbon nanotube/n-doped carbon nanosheet composite material with the sheet-like array structure obtained in example 1, and a scanning electron microscope image shows that one-dimensional CNTs are uniformly covered on two-dimensional Co-MOF, and the triangular morphology of MOF is preserved. Fig. 1(c) shows that the cobalt diselenide porous framework/nitrogen-doped carbon nanotube/carbon nanosheet composite material with the sheet-like array structure obtained in example 1 has a substantially unchanged morphology, which indicates that the selenylation process has little influence on the morphology, and further proves that the self-supporting porous structure is constructed by a large number of porous selenide sheets, one-dimensional CNTs and carbon nanosheets; porous CoSe2The surface of the carbon cloth had been fully covered and no porous CoSe was found2Agglomeration phenomenon, which visually proves the porous CoSe2And CNTs are homogeneously compounded. FIG. 1(d, e) TEM image shows uniform distribution of CNTsIn a two-dimensional selenide sheet, and the lattice stripes correspond to CoSe2Proves that the synthetic substance is CoSe2A material. FIG. 1(f) TEM element distribution chart showing the uniform distribution of C element, N element, Co element and Se element in the sample, further assisting in proving porous CoSe2And the uniform distribution of CNTs in the carbon cloth.
As shown in fig. 2, the sheet array structure cobalt diselenide porous frame/nitrogen-doped carbon nanotube/carbon nanosheet composite material is used as a zinc-air battery positive electrode material, and the prepared zinc-air battery has high specific energy and excellent cycling stability. At a current density of 5mA cm-2The cycle time of (3) is greater than 450 hours. As shown in fig. 3, it was assembled into a flexible zinc-air battery which can light led bulbs under conditions of bending 60 degrees, 120 degrees, and 180 degrees, and still maintain excellent cycle stability under the bent conditions.
Example 2
(1) The carbon cloth is sequentially soaked in acetone (99.5%), 10% hydrochloric acid and ethanol (99.7%), then washed to be neutral by deionized water, dried for 24 hours in vacuum at 60 ℃ and finally subjected to plasma hydrophilization for later use. 40mL of an aqueous solution containing 1.3g of dimethylimidazole was added to 40mL of an aqueous solution containing 0.5821g of cobalt nitrate hexahydrate at room temperature, and the mixture was mixed uniformly with magnetic stirring, added to the above carbon cloth and reacted at room temperature for 4 hours. After the reaction is finished, the mixture is washed for 3 times by deionized water. After the obtained product is dried in vacuum at 60 ℃ for 24 hours, growing Co-MOF in situ on carbon cloth;
(2) growing nitrogen-doped carbon nanotubes/nitrogen-doped carbon nanosheets on the carbon cloth treated in the step (1) by a CVD method: introducing nitrogen, heating to 500 ℃ at the speed of 3 ℃/min, introducing hydrogen and ethanol, calcining for 30 minutes, introducing nitrogen, keeping at 500 ℃ for 1.5 hours, and naturally cooling to room temperature under the protection of nitrogen to obtain the Co/nitrogen-doped carbon nanotube/nitrogen-doped carbon nanosheet with the array structure;
(3) adding selenium powder into the Co/nitrogen-doped carbon nano tube/nitrogen-doped carbon nano sheet growing on the surface of the carbon cloth in the step (2), introducing hydrogen, heating to 300 ℃ at the rate of 5 ℃ per minute, calcining for 6 hours, and finally naturally cooling to obtain the cobalt diselenide porous frame/nitrogen-doped carbon nano tube/carbon nano sheet composite material.
The sample in the embodiment is selected for characterization and analysis, and the test result is that the sheet array structure cobalt diselenide porous frame/nitrogen-doped carbon nanotube/carbon nanosheet composite material is used as the zinc-air battery anode material, so that the prepared zinc-air battery has high specific energy and excellent cycle stability. At a current density of 5mA cm-2The cycle time of (3) is greater than 350 hours.
Example 3
(1) The carbon cloth is sequentially soaked in acetone (99.5%), 10% hydrochloric acid and ethanol (99.7%), then washed to be neutral by deionized water, dried for 24 hours in vacuum at 60 ℃ and finally subjected to plasma hydrophilization for later use. 40mL of an aqueous solution containing 1.3g of dimethylimidazole was added to 40mL of an aqueous solution containing 0.5821g of cobalt nitrate hexahydrate at room temperature, and the mixture was mixed uniformly with magnetic stirring, added to the above carbon cloth and reacted at room temperature for 4 hours. After the reaction is finished, the mixture is washed for 3 times by deionized water. Vacuum drying the obtained product at 60 ℃ for 24h, and finally growing Co-MOF in situ on the carbon cloth;
(2) growing nitrogen-doped carbon nano tubes/nitrogen-doped carbon nano sheets on the carbon cloth treated in the step (1) by a CVD (chemical vapor deposition) method, introducing nitrogen, heating to 500 ℃ at the speed of 3 ℃/min, introducing hydrogen and ethanol, calcining for 10 minutes, introducing nitrogen, keeping at 500 ℃ for 2 hours, and naturally cooling to room temperature under the protection of nitrogen to obtain Co/nitrogen-doped carbon nano tubes/nitrogen-doped carbon nano sheets with an array structure;
(3) and (3) adding 0.7g of selenium powder into the Co/nitrogen-doped carbon nano tube/nitrogen-doped carbon nano sheet growing on the surface of the carbon cloth in the step (2), introducing hydrogen, heating to 600 ℃ at the rate of 5 ℃ per minute, calcining for 3 hours, and finally naturally cooling to obtain the cobalt diselenide porous frame/nitrogen-doped carbon nano tube/carbon nano sheet composite material with the sheet array structure.
The sample in the embodiment is selected for characterization and analysis, and the test result is that the sheet array structure cobalt diselenide porous frame/nitrogen-doped carbon nanotube/carbon nanosheet composite material is used as the zinc-air battery anode material, so that the prepared zinc-air battery has high specific energy and excellent cycle stability.At a current density of 5mA cm-2Under the test conditions of (2), the cycle time is greater than 400 hours.
Example 4
(1) Soaking carbon cloth in acetone, 10% hydrochloric acid and ethanol, washing with deionized water to neutrality, vacuum drying at 60 deg.C for 24 hr, and performing plasma hydrophilization treatment. 40mL of an aqueous solution containing 1.3g of dimethylimidazole was added to 40mL of an aqueous solution containing 0.5821g of cobalt nitrate hexahydrate at room temperature, and the mixture was mixed uniformly with magnetic stirring, added to the above carbon cloth and reacted at room temperature for 4 hours. After the reaction is finished, the mixture is washed for 3 times by deionized water. After the obtained product is dried in vacuum at 60 ℃ for 24 hours, growing Co-MOF in situ on carbon cloth;
(2) growing nitrogen-doped carbon nanotubes/nitrogen-doped carbon nanosheets on the carbon cloth treated in the step (1) by a CVD method: introducing nitrogen, heating to 600 ℃ at the speed of 5 ℃/min, introducing hydrogen and ethanol, calcining for 10 minutes, introducing nitrogen, keeping at 600 ℃ for 1 hour, and naturally cooling to room temperature under the protection of nitrogen to obtain the Co/nitrogen-doped carbon nanotube/nitrogen-doped carbon nanosheet with the array structure; (3) adding 0.5g of selenium powder, introducing hydrogen, heating to 450 ℃ at the rate of 5 ℃ per minute, calcining for 2 hours, and finally naturally cooling to obtain the flaky array structure cobalt diselenide porous frame/nitrogen-doped carbon nanotube/carbon nanosheet composite material.
The sample in the embodiment is selected for characterization and analysis, and the test result is that the sheet array structure cobalt diselenide porous frame/nitrogen-doped carbon nanotube/carbon nanosheet composite material is used as the zinc-air battery anode material, so that the prepared zinc-air battery has high specific energy and excellent cycle stability. At a current density of 5mA cm-2Under the test conditions of (1), the cycle time is greater than 250 hours.
Example 5
(1) Soaking carbon cloth in acetone, 10% hydrochloric acid and ethanol, washing with deionized water to neutrality, vacuum drying at 60 deg.C for 24 hr, and performing plasma hydrophilization treatment. 40mL of an aqueous solution containing 1.3g of dimethylimidazole was added to 40mL of an aqueous solution containing 0.5821g of cobalt nitrate hexahydrate at room temperature, and the mixture was mixed uniformly with magnetic stirring, added to the above carbon cloth and reacted at room temperature for 4 hours. After the reaction is finished, the mixture is washed for 3 times by deionized water. After the obtained product is dried in vacuum at 60 ℃ for 24 hours, growing Co-MOF in situ on carbon cloth;
(2) growing nitrogen-doped carbon nanotubes/nitrogen-doped carbon nanosheets on the carbon cloth treated in the step (1) by a CVD method: introducing nitrogen, heating to 500 ℃ at the speed of 3 ℃/min, introducing hydrogen and ethanol, calcining for 10 minutes, introducing nitrogen, keeping at 500 ℃ for 2 hours, and naturally cooling to room temperature under the protection of nitrogen to obtain the Co/nitrogen-doped carbon nanotube/nitrogen-doped carbon nanosheet with the array structure;
(3) and (3) adding 0.6g of selenium powder into the Co/nitrogen-doped carbon nano material growing on the surface of the carbon cloth in the step (2), introducing hydrogen, heating to 250 ℃ at the rate of 5 ℃ per minute, calcining for 6 hours, and finally naturally cooling to obtain the cobalt diselenide porous frame/nitrogen-doped carbon nano tube/carbon nano sheet composite material.
The sample in the embodiment is selected for characterization and analysis, and the test result is that the sheet array structure cobalt diselenide porous frame/nitrogen-doped carbon nanotube/carbon nanosheet composite material is used as the zinc-air battery anode material, so that the prepared zinc-air battery has high specific energy and excellent cycle stability. At a current density of 5mA cm-2Under the test conditions of (2), the cycle time is greater than 300 hours.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (9)
1. A preparation method of a cobalt diselenide/nitrogen-doped carbon nano material composite electrode catalytic material is characterized by comprising the following steps:
(1) growing Co-MOF in situ on the carbon cloth subjected to hydrophilization treatment by a hydrothermal method;
(2) growing a nitrogen-doped carbon nano material on the carbon cloth treated in the step (1) by a CVD (chemical vapor deposition) method to obtain a Co/nitrogen-doped carbon nano material; the nitrogen-doped carbon nano material is a combination of a nitrogen-doped carbon nano tube and a nitrogen-doped carbon nano sheet;
(3) and (3) selenizing the Co/nitrogen-doped carbon nano material grown on the surface of the carbon cloth in the step (2) to obtain the cobalt diselenide/nitrogen-doped carbon nano material composite electrode catalytic material.
2. The method for preparing a cobalt diselenide/nitrogen-doped carbon nanomaterial composite electrode catalytic material according to claim 1, wherein in the step (2), the CVD method specifically comprises: firstly introducing nitrogen to exhaust air, heating to 300-600 ℃ at the speed of 3-5 ℃/min, introducing ethanol and hydrogen to calcine for 0.1-1 h, then keeping for 1-3 h under the nitrogen atmosphere, and finally naturally cooling to obtain the Co/nitrogen-doped carbon nanomaterial.
3. The preparation method of the cobalt diselenide/nitrogen-doped carbon nanomaterial composite electrode catalytic material as claimed in claim 1, wherein in the step (3), the selenization treatment method comprises: selenium powder is added into the Co/nitrogen-doped carbon nano material, and the Co/nitrogen-doped carbon nano material is calcined for 1-20 hours at the temperature of 300-600 ℃.
4. The preparation method of the cobalt diselenide/nitrogen-doped carbon nanomaterial composite electrode catalytic material as claimed in claim 3, wherein the mass ratio of the selenium powder to the Co/nitrogen-doped carbon nanomaterial is 1: (8-10).
5. The preparation method of the cobalt diselenide/nitrogen-doped carbon nanomaterial composite electrode catalytic material as claimed in claim 1, wherein in the step (2), the length of the nitrogen-doped carbon nanotube is 50-200 nm.
6. The preparation method of the cobalt diselenide/nitrogen-doped carbon nanomaterial composite electrode catalytic material as claimed in claim 1, wherein in the step (2), the nitrogen-doped carbon nanosheet is of a triangular structure, and the side length of the nitrogen-doped carbon nanosheet is controlled to be 2-4 μm.
7. The preparation method of the cobalt diselenide/nitrogen-doped carbon nanomaterial composite electrode catalytic material of claim 1, wherein in the step (1), the Co-MOF is in a two-dimensional triangular structure.
8. A cobalt diselenide/nitrogen doped carbon nanomaterial composite electrode catalytic material prepared by the method of any one of claims 1 to 7.
9. The application of the cobalt diselenide/nitrogen-doped carbon nano material composite electrode catalytic material prepared by the method in any one of claims 1 to 7 in a zinc-air battery.
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