CN108767276B - Preparation method of nitrogen-doped porous carbon @ cobalt-based catalyst nanocage composite material for lithium-oxygen battery - Google Patents
Preparation method of nitrogen-doped porous carbon @ cobalt-based catalyst nanocage composite material for lithium-oxygen battery Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
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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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of a nitrogen-doped porous carbon @ cobalt-based catalyst nanocage composite material for a lithium-oxygen battery, which comprises the steps of firstly weighing 2-methylimidazole and metal cobalt salt, and respectively dissolving the 2-methylimidazole and the metal cobalt salt in a solvent to obtain a 2-methylimidazole solution and a metal cobalt salt solution; then dropwise adding the 2-methylimidazole solution into the metal cobalt salt solution, or dropwise adding the 2-methylimidazole solution and the metal cobalt salt solution into ethanol solvent at the same speed, standing for incubation, centrifugally separating the obtained product, repeatedly washing with ethanol, and drying to obtain block MOF; then putting the block MOF into a mixed solution of metal cobalt salt and metal zinc salt, reacting for 1-12 hours at the temperature of 60-150 ℃, then centrifugally separating the obtained product, repeatedly washing with ethanol, and drying to obtain the hollow MOF; then carbonizing the prepared hollow MOF under inert atmosphere; and finally, activating the powder obtained after carbonization in an air atmosphere to obtain the nitrogen-doped porous carbon @ cobalt-based catalyst nanocage composite material for the lithium-oxygen battery.
Description
Technical Field
The invention relates to the field of new energy materials, in particular to a preparation method of a nitrogen-doped porous carbon @ cobalt-based catalyst nanocage composite material for a lithium-oxygen battery.
Background
As chemical power sources (batteries) are widely used in various fields of human life, development and utilization of safe, green, and efficient secondary batteries have gradually become a global topic. The lithium air battery is particularly concerned with the ultrahigh theoretical energy density, has an open system, takes metal lithium as a negative electrode and oxygen in the external environment as a positive electrode, completes charging and discharging through oxygen reduction reaction and oxygen precipitation reaction, has the energy density about ten times that of the conventional lithium ion battery, has light weight and low operation cost, and is the most attractive day-to-day star. Once the lithium-air battery is successfully developed, the lithium-air battery has a profound influence on the related fields of portable equipment, energy storage devices and the like.
However, the problems of low capacity, poor magnification, short cycle life and the like of the existing lithium-air battery generally exist, and the reasons are mainly attributed to the fact that the inertia of a solid discharge product is strong and the battery has poor reaction kinetics. The structure of the air anode is reasonably designed, and the improvement of the reaction kinetics of the battery is an effective measure for improving the performance of the lithium-air battery.
Disclosure of Invention
The invention provides a preparation method of a nitrogen-doped porous carbon @ cobalt-based catalyst nanocage composite material for a lithium-oxygen battery, which aims to solve the problems of low capacity, poor magnification, short cycle life and the like of the conventional lithium-air battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a nitrogen-doped porous carbon @ cobalt-based catalyst nanocage composite material for a lithium-oxygen battery comprises the following steps:
(1) weighing 2-methylimidazole and metal cobalt salt, and respectively dissolving the 2-methylimidazole and the metal cobalt salt in a solvent to obtain a 2-methylimidazole solution and a metal cobalt salt solution;
(2) dropwise adding a 2-methylimidazole solution into a metal cobalt salt solution, or dropwise adding the 2-methylimidazole solution and the metal cobalt salt solution into an ethanol solvent at the same speed, standing for incubation, centrifugally separating the obtained product, repeatedly washing with ethanol, and drying to obtain a block MOF;
(3) putting the block MOF into a mixed solution of metal cobalt salt and metal zinc salt, reacting for 1-12 hours at the temperature of 60-150 ℃, then centrifugally separating the obtained product, repeatedly washing with ethanol, and drying to obtain the hollow MOF;
(4) carbonizing the prepared hollow MOF under an inert atmosphere;
(5) and activating the powder obtained after carbonization in an air atmosphere to obtain the nitrogen-doped porous carbon @ cobalt-based catalyst nanocage composite material for the lithium-oxygen battery.
Further, the concentration of the 2-methylimidazole solution and the concentration of the metal cobalt salt solution in the step (1) are both 20-80 mmol/L.
Further, the metal cobalt salt in the step (1) is cobalt nitrate salt, cobalt chloride salt or cobalt sulfate salt; the solvent in the step (1) is methanol, ethanol, water or a mixed solution of water and methanol or ethanol.
Further, the mass ratio of the 2-methylimidazole to the metal cobalt salt in the step (2) is 1:1, and the dropping speed in the step (2) is 5-100 m L/min.
Further, the standing time in the step (2) is 1 to 24 hours.
Further, the mixed solution of the metal cobalt salt and the metal zinc salt in the step (3) is obtained by dissolving the metal cobalt salt and the metal zinc salt into a solvent, wherein the mass ratio of the metal cobalt salt to the metal zinc salt is (10-90): (90-10).
Further, in the step (3), the metal cobalt salt is cobalt nitrate salt, cobalt chloride salt or cobalt sulfate salt, the metal zinc salt is zinc nitrate salt, zinc chloride salt or zinc sulfate salt, and the solvent is methanol, ethanol, water or a mixed solution of water and methanol or ethanol.
Further, the concentration of the mixed solution in the step (3) is 20-80 mmol/L, and after the bulk MOF is added into the mixed solution, the concentration of the bulk MOF is 10-90mg/m L.
Further, the carbonization temperature in the step (4) is 600-1000 ℃, and the carbonization time is 1-6 hours.
Further, the activation temperature in the step (5) is 30-400 ℃, and the activation time is 1-6 hours.
Compared with the prior art, the invention has the following beneficial technical effects:
according to the invention, cobalt salt and water-soluble nitrogen-containing organic ligand are used as raw materials, hollow MOF is synthesized in a solution system, and the nitrogen-doped porous carbon @ cobalt-based catalyst nanocage composite material is obtained through carbonization and activation treatmentThe composite material has micropores, mesopores and macropores, and the specific surface area is 1000-5000 m2g-1The nitrogen-doped carbon and cobalt-based catalyst in the material are uniformly dispersed, the product prepared by the method has a large specific surface area, the nano cage structure of the product can provide a deposition position for a solid discharge product and weaken the passivation of the anode, and meanwhile, the nitrogen-doped carbon material and the cobalt-based catalyst are uniformly dispersed, so that sufficient catalytic active sites can be provided, the maximum effect of the catalyst can be exerted, and the performance of the lithium-air battery can be improved; the composite material obtained by the invention can be used as a lithium-oxygen battery anode material to contain enough discharge products, and effectively improves the battery reaction kinetics, so that the battery not only has 10000mA h g-1The invention has the advantages of high specific capacity, excellent cycle and rate performance, simple preparation process, low cost, no toxic and harmful components in the preparation process, environment-friendly characteristic and capability of meeting the requirements of industrial production and use.
Detailed Description
Embodiments of the invention are described in further detail below:
a preparation method of a nitrogen-doped porous carbon @ cobalt-based catalyst nanocage composite material for a lithium-oxygen battery comprises the following steps: preparing a block MOF → derivation of a hollow MOF → carbonization → activation, and finally obtaining the three-dimensional nitrogen-doped porous carbon @ cobalt-based catalyst nanocage composite material. The block MOF is a dodecahedral ZIF-67 and is formed by compounding 2-methylimidazole and cobalt-containing metal salt, the hollow MOF structure is derived from the phase transfer process of the block MOF, the nanocage composite material is composed of a nitrogen-doped graphitized porous carbon material and cobalt-based catalyst nanoparticles, and the cobalt-based catalyst nanoparticles can be CoO and Co3O4One or two of them can be compounded, the cobalt-containing metal salt can be cobalt nitrate, cobalt chloride, cobalt sulfate, etc., and the solvent can be methanol, ethanol, water and water/alcohol mixed solution.
The method specifically comprises the following steps:
(1) weighing a certain amount of 2-methylimidazole and metal cobalt salt, respectively dissolving the 2-methylimidazole and the metal cobalt salt in a solvent to ensure that the concentrations of the metal salt and the metal cobalt salt are 20-80 mmol/L, wherein the metal salt is one of nitrate, chloride and sulfate, and the solvent can be methanol, ethanol, water and water/alcohol mixed solution.
(2) Dropping a 2-methylimidazole solution into a metal salt solution at a certain speed (single drop), or dropping the 2-methylimidazole solution and the metal salt solution into an ethanol solvent at the same speed, wherein the dropping speed is 5-100 m L/min, the mass ratio of the 2-methylimidazole to the metal cobalt salt is 1:1, standing for 1-24 hours to hatch to generate a block MOF, centrifugally separating the obtained product, repeatedly washing with ethanol and then drying, wherein the drying mode can be common drying, vacuum drying or freeze drying.
(3) Putting a certain amount of block MOF into a metal cobalt/zinc mixed solution, wherein the mass ratio of a metal cobalt salt to a metal zinc salt is (10-90): (90-10), the concentration of the mixed solution is 20-80 mmol/L, the concentration of the block MOF in the mixed solution is 10-90mg/m L, the metal salt can be nitrate, chloride and sulfate, the solvent can be methanol, ethanol, water and water/alcohol mixed solution, the ambient temperature is 60-150 ℃, the reaction time is 1-12 hours, then centrifuging and separating the obtained product, repeatedly washing with ethanol, and drying, wherein the drying mode can be common drying, vacuum drying or freeze drying.
(4) Carbonizing the prepared hollow MOF in an inert atmosphere, wherein the inert atmosphere is argon, nitrogen or argon-hydrogen mixed gas, the carbonization temperature is 600-1000 ℃, and the carbonization time is 1-6 hours.
(5) Activating the powder obtained after carbonization in the air to change the surface metal of the powder into oxide with higher catalytic activity, wherein the activation temperature is 30-400 ℃, and the activation time is 1-6 hours.
According to the invention, the porous carbon structure with the high specific surface can provide a gas transmission channel for oxygen diffusion, and simultaneously provide a storage space for a discharge product, and researches show that the noble metal, the perovskite, the transition metal oxide, the mixed element (N, S) doping modification and the like can reduce the reaction energy barrier of the battery to a certain extent and improve the reaction kinetics. The metal organic framework Material (MOF) has the advantages of convenient synthesis, low cost and porous structure, porous nitrogen-doped carbon (N-C) can be obtained by pyrolyzing the material, metal elements in the material are changed into metal particles in the pyrolysis process, and the metal particles and the N-C in the material bulk phase are uniformly distributed. Meanwhile, the MOF material can realize the construction of a hollow structure by depending on phase transition, and is a simple and convenient effective method for preparing the nitrogen-doped nano cage carbon material.
The nitrogen-doped carbon nanocage material can enable a solid product to be deposited in a limited space, the passivation behavior of a positive electrode is reduced, the nitrogen-doped carbon material has excellent catalytic properties, the promotion of the reaction kinetics of the battery can be accelerated, the uniform compounding and effective dispersion of a metal catalyst (such as cobalt-based oxide) and the carbon material are a main problem in the preparation of the positive electrode nanocomposite at present, the uniform dispersion of metal elements in the MOF enables the metal oxide catalyst to be uniformly dispersed after carbonization and activation, the hollow MOF is used for preparing the three-dimensional nitrogen-doped porous carbon @ cobalt-based catalyst nanocage composite material, and the performance of the lithium air battery can be promoted by means of the synergistic effect among the nitrogen-doped carbon material, the metal oxide and the nanocage structure.
The present invention is described in further detail below with reference to examples:
example 1
Respectively weighing 50mg of 2-methylimidazole and cobalt nitrate, respectively dissolving the 2-methylimidazole solution and the cobalt nitrate in methanol to enable the concentrations to be 20 mmol/L, dripping the 2-methylimidazole solution into a metal cobalt salt solution at the speed of 100m L/min, standing for 12 hours to generate block MOF, centrifugally separating the obtained product, repeatedly washing with ethanol, drying at the temperature of 60 ℃ in vacuum, weighing 50mg of block MOF, putting the block MOF into a 60 mmol/L cobalt nitrate/zinc methanol solution, wherein the mass ratio of the metal cobalt salt to the metal zinc salt is 10: 90, the concentration of the block MOF in the mixed solution is 10mg/m L, reacting at the temperature of 100 ℃ for 6 hours, centrifugally separating the obtained product, repeatedly washing with ethanol, drying at the temperature of 60 ℃ to obtain hollow MOF, carbonizing at the temperature of 800 ℃ under nitrogen for 6 hours, and finally activating at the temperature of 300 ℃ under air for 4 hours to obtain the three-dimensional nitrogen-doped Co @ porous carbon3O4A nanocage composite.
The specific surface area of the material prepared in example 1 was 2000m2g-1P for composite materialVDF adhesive is coated on the foamed nickel to prepare the air anode and assemble the lithium air battery, and the specific discharge capacity of the battery is 15000mA h g under pure oxygen atmosphere-1And the capacity retention rate reaches 85 percent after 30 times of circulation.
Example 2
Respectively weighing 50mg of 2-methylimidazole and cobalt nitrate, respectively dissolving the 2-methylimidazole solution and the cobalt nitrate in methanol to enable the concentrations to be 80 mmol/L, dripping the 2-methylimidazole solution into a metal cobalt salt solution at the speed of 5m L/min, standing for 24 hours to generate block MOF, centrifugally separating the obtained product, repeatedly washing the product with ethanol, drying the product at the temperature of 60 ℃ in vacuum, weighing 30mg of block MOF, putting the block MOF into an 80 mmol/L cobalt nitrate/zinc methanol solution, wherein the mass ratio of the metal cobalt salt to the metal zinc salt is 90: 10, the concentration of the block MOF in the mixed solution is 90mg/m L, reacting at the temperature of 100 ℃ for 6 hours, centrifugally separating the obtained product, repeatedly washing the product with ethanol, drying the product at the temperature of 60 ℃ in vacuum to obtain hollow MOF, carbonizing the hollow MOF at the temperature of 600 ℃ under nitrogen for 6 hours, and finally activating the porous carbon at the temperature of 300 ℃ under air for 4 hours to obtain the3O4A nanocage composite.
Example 2 the material prepared has a specific surface area of 2200m2g-1Coating the composite material on foamed nickel by using a PVDF (polyvinylidene fluoride) adhesive to prepare an air anode and assembling the air anode into a lithium-air battery, wherein the specific discharge capacity of the battery is 17000mA h g under pure oxygen atmosphere-1And the capacity retention rate reaches 80 percent after 50 times of circulation.
Example 3
Respectively weighing 50mg of 2-methylimidazole and cobalt chloride, respectively dissolving the 2-methylimidazole solution and the cobalt chloride in methanol to enable the concentrations to be 40 mmol/L, dripping the 2-methylimidazole solution into a metal cobalt salt solution at the speed of 30m L/min, standing for 1 hour to generate block MOF, centrifugally separating the obtained product, repeatedly washing the product with ethanol, drying the product at the temperature of 60 ℃ in vacuum, weighing 20mg of block MOF, putting the block MOF into a 20 mmol/L cobalt chloride/zinc ethanol solution, wherein the mass ratio of the metal cobalt salt to the metal zinc salt is 50: 50, the concentration of the block MOF in the mixed solution is 60mg/m L, reacting at the temperature of 100 ℃ for 6 hours, centrifugally separating the obtained product, repeatedly washing the product with ethanol, drying the product at the temperature of 60 ℃ to obtain hollow MOF, and finally drying the hollow MOF in the mixed solution atCarbonizing at 1000 deg.C for 1 hr under nitrogen. Finally, activating for 4 hours at 300 ℃ in the air to obtain three-dimensional nitrogen-doped porous carbon @ Co3O4A nanocage composite.
Example 3 the material prepared has a specific surface area of 1900m2g-1Coating the composite material on foamed nickel by using a PVDF (polyvinylidene fluoride) adhesive to prepare an air anode and assembling the air anode into a lithium-air battery, wherein the specific discharge capacity of the battery under pure oxygen atmosphere is 14000mA h g-1And the capacity retention rate reaches 85 percent after 50 times of circulation.
Example 4
Respectively weighing 50mg of 2-methylimidazole and cobalt sulfate, respectively dissolving the 2-methylimidazole solution and the cobalt sulfate in methanol to enable the concentrations to be 60 mmol/L, dripping the 2-methylimidazole solution into a metal cobalt salt solution at the speed of 70m L/min, standing for 12 hours to generate block MOF, centrifugally separating the obtained product, repeatedly washing with ethanol, drying at the temperature of 60 ℃ in vacuum, weighing 40mg of block MOF, putting the block MOF into a 60 mmol/L cobalt sulfate/zinc aqueous solution, wherein the mass ratio of the metal cobalt salt to the metal zinc salt is 40: 90, the concentration of the block MOF in the mixed solution is 50mg/m L, reacting at the temperature of 100 ℃ for 6 hours, centrifugally separating the obtained product, repeatedly washing with ethanol, drying at the temperature of 60 ℃ to obtain hollow MOF, carbonizing at the temperature of 800 ℃ for 4 hours under nitrogen, and finally activating at the temperature of 300 ℃ for 4 hours under air to obtain the three-dimensional nitrogen-doped @ porous carbon Co3O4A nanocage composite.
Example 4 the material prepared has a specific surface area of 2000m2g-1Coating the composite material on foamed nickel by using a PVDF (polyvinylidene fluoride) adhesive to prepare an air anode and assembling the air anode into a lithium-air battery, wherein the specific discharge capacity of the battery is 18000mA h g under pure oxygen atmosphere-1And the capacity retention rate reaches 70% after 100 cycles.
Example 5
Respectively weighing 50mg of 2-methylimidazole and cobalt chloride, respectively dissolving the 2-methylimidazole and the cobalt chloride in methanol to ensure that the concentrations of the 2-methylimidazole and the cobalt chloride are 40 mmol/L, dripping the 2-methylimidazole solution into a metal cobalt salt solution at the speed of 30m L/min, standing for 12 hours to generate block MOF, centrifugally separating the obtained product, repeatedly washing the product with ethanol, drying the product at the temperature of 60 ℃ in vacuum, weighing 20mg of block MOF, and placing the block MOFAdding the mixture into 80 mmol/L cobalt chloride/zinc ethanol solution, wherein the mass ratio of metal cobalt salt to metal zinc salt is 50: 50, the concentration of block MOF in the mixed solution is 70mg/m L, reacting for 12 hours at 60 ℃, then centrifugally separating the obtained product, repeatedly washing with ethanol, drying at 60 ℃ in vacuum to obtain hollow MOF, carbonizing for 4 hours at 700 ℃ under nitrogen, and finally activating for 6 hours at 400 ℃ under air to obtain three-dimensional nitrogen-doped porous carbon Co @ Co3O4A nanocage composite.
Example 5 the material prepared has a specific surface area of 2100m2g-1Coating the composite material on foamed nickel by using a PVDF (polyvinylidene fluoride) adhesive to prepare an air anode and assembling the air anode into a lithium-air battery, wherein the specific discharge capacity of the battery under pure oxygen atmosphere is 13000mA h g-1And the capacity retention rate reaches 80 percent after 100 cycles.
Example 6
Respectively weighing 50mg of 2-methylimidazole and cobalt chloride, respectively dissolving the 2-methylimidazole solution and the cobalt chloride in methanol to enable the concentrations of the 2-methylimidazole solution and the cobalt chloride to be 40 mmol/L, dropwise adding the 2-methylimidazole solution into a metal cobalt salt solution at the speed of 30m L/min, standing for 12 hours to generate a block MOF, centrifugally separating the obtained product, repeatedly washing with ethanol, drying at 60 ℃ in vacuum, weighing 20mg of the block MOF, putting the block MOF into a 40 mmol/L cobalt chloride/zinc ethanol solution, wherein the mass ratio of the metal cobalt salt to the metal zinc salt is 50: 50, the concentration of the block MOF in the mixed solution is 40mg/m L, reacting at 150 ℃ for 1 hour, centrifugally separating the obtained product, repeatedly washing with ethanol, drying at 60 ℃ in vacuum to obtain a hollow MOF, carbonizing at 900 ℃ under nitrogen for 3 hours, and finally activating at 30 ℃ under air for 4 hours to obtain the nitrogen-doped porous carbon nano cage composite material.
Example 6 the material prepared has a specific surface area of 2000m2g-1Coating the composite material on foamed nickel by using a PVDF (polyvinylidene fluoride) adhesive to prepare an air anode and assembling the air anode into a lithium air battery, wherein the specific discharge capacity of the battery is 10000mA h g under pure oxygen atmosphere-1And the capacity retention rate reaches 75 percent after 50 times of circulation.
Claims (10)
1. A preparation method of a nitrogen-doped porous carbon @ cobalt-based catalyst nanocage composite material for a lithium-oxygen battery is characterized by comprising the following steps of:
(1) weighing 2-methylimidazole and metal cobalt salt, and respectively dissolving the 2-methylimidazole and the metal cobalt salt in a solvent to obtain a 2-methylimidazole solution and a metal cobalt salt solution;
(2) dripping 2-methylimidazole solution into a metal cobalt salt solution, or dripping the 2-methylimidazole solution and the metal cobalt salt solution into ethanol solvent at the same speed, standing for incubation, centrifugally separating the obtained product, repeatedly washing with ethanol, and drying to obtain block MOF;
(3) putting the block MOF into a mixed solution of metal cobalt salt and metal zinc salt, reacting for 1-12 hours at the temperature of 60-150 ℃, then centrifugally separating the obtained product, repeatedly washing with ethanol, and drying to obtain the hollow MOF;
(4) carbonizing the prepared hollow MOF under an inert atmosphere;
(5) and activating the powder obtained after carbonization in an air atmosphere to obtain the nitrogen-doped porous carbon @ cobalt-based catalyst nanocage composite material for the lithium-oxygen battery.
2. The preparation method of the nitrogen-doped porous carbon @ cobalt-based catalyst nanocage composite material for the lithium-oxygen battery as claimed in claim 1, wherein the concentration of the 2-methylimidazole solution and the concentration of the metal cobalt salt solution in step (1) are both 20-80 mmol/L.
3. The preparation method of the lithium-oxygen battery nitrogen-doped porous carbon @ cobalt-based catalyst nanocage composite material according to claim 1, wherein the metal cobalt salt in the step (1) is cobalt nitrate salt, cobalt chloride salt or cobalt sulfate salt; the solvent in the step (1) is methanol, ethanol, water or a mixed solution of water and methanol or ethanol.
4. The preparation method of the nitrogen-doped porous carbon @ cobalt-based catalyst nanocage composite material for the lithium-oxygen battery as claimed in claim 1, wherein the mass ratio of 2-methylimidazole to metal cobalt salt in the step (2) is 1:1, and the dropping rate in the step (2) is 5-100 m L/min.
5. The preparation method of the nitrogen-doped porous carbon @ cobalt-based catalyst nanocage composite material for the lithium-oxygen battery as claimed in claim 1, wherein the standing time in the step (2) is 1-24 hours.
6. The preparation method of the nitrogen-doped porous carbon @ cobalt-based catalyst nanocage composite material for the lithium-oxygen battery as claimed in claim 1, wherein the mixed solution of the metal cobalt salt and the metal zinc salt in the step (3) is obtained by dissolving the metal cobalt salt and the metal zinc salt in a solvent, wherein the mass ratio of the metal cobalt salt to the metal zinc salt is (10-90): (90-10).
7. The preparation method of the nitrogen-doped porous carbon @ cobalt-based catalyst nanocage composite material for the lithium-oxygen battery as claimed in claim 6, wherein in the step (3), the metal cobalt salt is cobalt nitrate, cobalt chloride or cobalt sulfate, the metal zinc salt is zinc nitrate, zinc chloride or zinc sulfate, and the solvent is methanol, ethanol, water or a mixed solution of water and methanol or ethanol.
8. The preparation method of the nitrogen-doped porous carbon @ cobalt-based catalyst nanocage composite material for the lithium-oxygen battery as claimed in claim 1, wherein the concentration of the mixed solution in the step (3) is 20-80 mmol/L, and after the bulk MOF is added into the mixed solution, the concentration of the bulk MOF is 10-90mg/m L.
9. The preparation method of the nitrogen-doped porous carbon @ cobalt-based catalyst nanocage composite material for the lithium-oxygen battery as claimed in claim 1, wherein the carbonization temperature in the step (4) is 600-1000 ℃, and the carbonization time is 1-6 hours.
10. The preparation method of the nitrogen-doped porous carbon @ cobalt-based catalyst nanocage composite material for the lithium-oxygen battery as claimed in claim 1, wherein the activation temperature in the step (5) is 30-400 ℃, and the activation time is 1-6 hours.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105609322A (en) * | 2015-12-21 | 2016-05-25 | 中南大学 | Cobalt selenide/nitrogen-doped carbon composite material and preparation method and application therefor |
| CN106058215A (en) * | 2016-08-05 | 2016-10-26 | 中南大学 | Dodecahedral porous Co3ZnC/C composite material preparation method and use of dodecahedral porous Co3ZnC/C composite material in lithium ion battery |
| CN106229518A (en) * | 2016-07-26 | 2016-12-14 | 北京工业大学 | A kind of preparation method constructing hollow polyhedral ZnS/CoS eelctro-catalyst based on MOF template |
| CN106544693A (en) * | 2016-11-28 | 2017-03-29 | 北京工业大学 | A kind of preparation of multilevel hierarchy ZnO@CoS membrane electrodes and its application in photoelectric decomposition water |
| WO2017123162A1 (en) * | 2016-01-14 | 2017-07-20 | Agency For Science, Technology And Research | Free-standing mof-derived hybrid porous carbon nanofiber mats |
-
2018
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105609322A (en) * | 2015-12-21 | 2016-05-25 | 中南大学 | Cobalt selenide/nitrogen-doped carbon composite material and preparation method and application therefor |
| WO2017123162A1 (en) * | 2016-01-14 | 2017-07-20 | Agency For Science, Technology And Research | Free-standing mof-derived hybrid porous carbon nanofiber mats |
| CN106229518A (en) * | 2016-07-26 | 2016-12-14 | 北京工业大学 | A kind of preparation method constructing hollow polyhedral ZnS/CoS eelctro-catalyst based on MOF template |
| CN106058215A (en) * | 2016-08-05 | 2016-10-26 | 中南大学 | Dodecahedral porous Co3ZnC/C composite material preparation method and use of dodecahedral porous Co3ZnC/C composite material in lithium ion battery |
| CN106544693A (en) * | 2016-11-28 | 2017-03-29 | 北京工业大学 | A kind of preparation of multilevel hierarchy ZnO@CoS membrane electrodes and its application in photoelectric decomposition water |
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