CN108767276A - A kind of preparation method of lithium-oxygen battery N doping porous carbon@cobalt-base catalyst nanocages composite materials - Google Patents
A kind of preparation method of lithium-oxygen battery N doping porous carbon@cobalt-base catalyst nanocages composite materials 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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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- 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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
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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 kind of preparation methods of lithium-oxygen battery N doping porous carbon@cobalt-base catalyst nanocages composite materials, weigh 2-methylimidazole and Cobalt salts first, are dissolved in solvent respectively, obtain 2-methylimidazole solution and Cobalt salts solution；Then by 2-methylimidazole solution to be added drop-wise in Cobalt salts solution, or 2-methylimidazole solution and Cobalt salts solution are added drop-wise in alcohol solvent at the same rate, it is then allowed to stand hatching, products therefrom is centrifuged, block MOF is dried to obtain after being used in combination ethyl alcohol to wash repeatedly；Then block MOF is put into Cobalt salts and metallic zinc mixed salt solution, is reacted 1-12 hours at a temperature of 60-150 DEG C, then products therefrom is centrifuged, hollow MOF is dried to obtain after being used in combination ethyl alcohol to wash repeatedly；Then the hollow MOF of preparation is carbonized under an inert atmosphere；Finally the powder obtained after carbonization is activated in air atmosphere to get to lithium-oxygen battery N doping porous carbon@cobalt-base catalyst nanocages composite materials.
Description
Technical field
The present invention relates to new energy materials fields, and in particular to a kind of lithium-oxygen battery N doping porous carbon@cobalt-base catalysts
The preparation method of nanocages composite material.
Background technology
As electrochmical power source (battery) is widely used in the every field of human lives, safety, green, high efficient secondary battery
Development and utilization be increasingly becoming a global task.Wherein lithium-air battery is especially received with its superelevation theoretical energy density
Concern, lithium-air battery has open system, and using lithium metal as cathode, the oxygen in external environment is anode, by the way that oxygen occurs
Reduction reaction and oxygen evolution reaction complete charge and discharge, and energy density is about ten times of traditional lithium-ion battery, and light weight, fortune
Row is at low cost, is the rising star of most attraction.It, will be to portable equipment, energy storage device once lithium-air battery is succeeded in developing
Etc. related fields bring far-reaching influence.
However the problems such as lithium-air battery generally existing capacity is low at present, difference of magnification, short cycle life, reason is mainly returned
Because in solid-state discharge product strong inert, there are poor kineticses for battery.The structure of air cathode is rationally designed, electricity is promoted
Pond kinetics is to promote an effective measures of lithium-air battery performance.
Invention content
The present invention provides a kind of preparation side of lithium-oxygen battery N doping porous carbon@cobalt-base catalyst nanocages composite materials
Method, the problems such as to overcome the low capacity that existing lithium-air battery faces, difference of magnification, short cycle life, the present invention is easy, quickly,
Solve the problems, such as that catalytic active substance is evenly dispersed and solid-state discharge product deposition causes anode to be passivated.
In order to achieve the above objectives, the present invention adopts the following technical scheme that：
A kind of preparation method of lithium-oxygen battery N doping porous carbon@cobalt-base catalyst nanocages composite materials, including it is following
Step：
(1) 2-methylimidazole and Cobalt salts are weighed, is dissolved in solvent respectively, 2-methylimidazole solution and metallic cobalt are obtained
Salting liquid；
(2) by 2-methylimidazole solution to be added drop-wise in Cobalt salts solution, or by 2-methylimidazole solution and metallic cobalt
Salting liquid is added drop-wise in alcohol solvent at the same rate, is then allowed to stand hatching, products therefrom is centrifuged, and is used in combination ethyl alcohol anti-
After backwashing is dried to obtain block MOF after washing；
(3) block MOF is put into the mixed solution of Cobalt salts and metal zinc salt, reacts 1- at a temperature of 60-150 DEG C
12 hours, then products therefrom is centrifuged, hollow MOF is dried to obtain after being used in combination ethyl alcohol to wash repeatedly；
(4) the hollow MOF of preparation is carbonized under an inert atmosphere；
(5) powder obtained after carbonization is activated in air atmosphere to get to lithium-oxygen battery N doping porous carbon@
Cobalt-base catalyst nanocages composite material.
Further, the concentration of 2-methylimidazole solution and Cobalt salts solution is 20-80mmol/L in step (1).
Further, Cobalt salts are nitric acid cobalt salt, chlorination cobalt salt or sulfuric acid cobalt salt in step (1)；Solvent in step (1)
For the mixed solution of methanol, ethyl alcohol, water or water and methanol or ethyl alcohol.
Further, the mass ratio of 2-methylimidazole and Cobalt salts is 1 in step (2):1, and speed is added dropwise in step (2)
Rate is 5~100mL/min.
Further, time of repose is 1-24 hours in step (2).
Further, Cobalt salts and metallic zinc mixed salt solution are that Cobalt salts and metal zinc salt are molten in step (3)
Enter solvent to obtain, wherein the mass ratio of Cobalt salts and metal zinc salt is (10-90)：(90-10).
Further, Cobalt salts are nitric acid cobalt salt, chlorination cobalt salt or sulfuric acid cobalt salt in step (3), and metal zinc salt is nitre
Sour zinc salt, chlorination zinc salt or sulfuric acid zinc salt, solvent are the mixed solution of methanol, ethyl alcohol, water or water and methanol or ethyl alcohol.
Further, in step (3) mixed solution a concentration of 20-80mmol/L, block MOF is added in mixed solution
Afterwards, a concentration of 10-90mg/mL of block MOF.
Further, carburizing temperature is 600-1000 DEG C in step (4), and carbonization time is 1-6 hours.
Further, activation temperature is 30-400 DEG C in step (5), and soak time is 1-6 hours.
Compared with prior art, the present invention has technique effect beneficial below：
The present invention synthesizes hollow MOF in solution system, passes through carbon using cobalt salt and water-soluble nitrogenous organic ligand as raw material
Change and activation process obtain N doping porous carbon@cobalt-base catalyst nanocages composite materials, the composite material not only there is micropore but also
With mesoporous and macropore, specific surface area is in 1000~5000m2g-1, nitrogen-doped carbon and cobalt-base catalyst are evenly dispersed in material, this
There is product prepared by invention large specific surface area, nanometer basket structure can provide deposition position for solid-state discharge product, subtract
Weak positive pole passivation, meanwhile, nitrogen-doped carbon material and cobalt-base catalyst are evenly dispersed, can provide sufficient active site,
The maximum effect for being conducive to play catalyst, is conducive to the promotion of lithium-air battery performance；The composite material that the present invention is obtained is used
Enough discharging products can be accommodated by making lithium-oxygen battery positive electrode, and effectively promote cell reaction dynamics so that battery is not
Only there is 10000mA h g-1Height ratio capacity, while there is excellent cycle and high rate performance, and preparation process of the present invention letter
Single, of low cost, preparation process nonhazardous ingredient has environmental-friendly characteristic, the needs that can meet industrialized production and use.
Specific implementation mode
Embodiments of the present invention are described in further detail below：
A kind of preparation method of lithium-oxygen battery N doping porous carbon@cobalt-base catalyst nanocages composite materials, according to following
Step carries out：Development → carbonization → activation of the preparation of block MOF → hollow MOF finally obtains three-dimensional N doping porous carbon@cobalts
Base catalyst nano cage composite material.Block MOF is the ZIF-67 of dodecahedron, compound by 2-methylimidazole and metal salt containing cobalt
It forms, hollow MOF structures are derived from the block MOF phase transition behaviors of itself, and nanocages composite material is graphitized more by N doping
Hole carbon material and cobalt-base catalyst nano particle two parts composition, cobalt-base catalyst nano particle can be CoO and Co3O4In
It is a kind of, or two kinds therein compound, and metal salt containing cobalt can be cobalt nitrate, cobalt chloride, cobaltous sulfate etc., and solvent can be
Methanol, ethyl alcohol, Shui Heshui/mixed alkoxide solution.
Specifically include following steps：
(1) a certain amount of 2-methylimidazole and Cobalt salts are weighed, are dissolved in solvent respectively, it is 20- to make its concentration
80mmol/L.The metal salt is nitrate, chlorate, one kind in sulfate, solvent can be methanol, ethyl alcohol, Shui Heshui/
Mixed alkoxide solution.
(2) 2-methylimidazole solution is added drop-wise in metal salt solution with given pace (single to drip), or by 2-methylimidazole
Solution and metal salt solution instill in alcohol solvent at the same rate, and drop rate is 5~100mL/min, wherein 2- first
The mass ratio of base imidazoles and Cobalt salts is 1:1, it is then allowed to stand hatching in 1-24 hours and generates block MOF, products therefrom is centrifuged
Separation, dry after being used in combination ethyl alcohol to wash repeatedly, dry mode can be normal drying, vacuum drying, or freezing is dry
It is dry.
(3) a certain amount of block MOF is put into metallic cobalt/zinc mixed solution, the wherein quality of Cobalt salts and metal zinc salt
Than for (10-90)：(90-10), a concentration of 20-80mmol/L of mixed solution, and block MOF is a concentration of in mixed solution
10-90mg/mL, metal salt can be nitrate, chlorate, sulfate, and solvent can be methanol, ethyl alcohol, Shui Heshui/alcohol mixing
Solution, environment temperature are 60-150 DEG C, and the reaction time is 1-12 hours.Then products therefrom is centrifuged, is used in combination ethyl alcohol anti-
After backwashing is dry after washing, and dry mode can be normal drying, vacuum drying, or freeze-drying.
(4) the hollow MOF of preparation is carbonized under an inert atmosphere, inert atmosphere is argon gas, nitrogen or the mixing of argon hydrogen
Gas, carburizing temperature are 600-1000 DEG C, and carbonization time is 1-6 hours.
(5) powder obtained after carbonization is activated under air, so that its surface metal is become catalytic activity higher
Oxide, activation temperature are 30-400 DEG C, and soak time is 1-6 hours.
The porous carbon structure of high-ratio surface can provide gas delivery passage for the diffusion of oxygen in the present invention, while to put
Electric product provides memory space, and research shows that noble metal, perovskite, transition metal oxide, miscellaneous element (N, S) doping vario-property
Etc. can reduce cell reaction energy barrier to a certain extent, kinetics is promoted.Metal-organic framework material (MOF), which has, closes
At convenient, cheap, structural porous, which can be obtained porous nitrogen-doped carbon (N-C) and its interior metal element through pyrolysis
It is metallic particles to develop in pyrolytic process, and metallic particles, N-C are evenly distributed in material bodies phase.MOF materials itself can be with simultaneously
The structure that hollow-core construction is realized by phase transition, is a kind of effective ways for preparing nitrogen-doped nanometer cage carbon material of simplicity.
Nitrogen-doped nanometer cage carbon material can make solid product be deposited in confinement space, mitigate positive passivation behavior,
And nitrogen-doped carbon material itself has excellent catalysis characteristics, can accelerate the dynamic (dynamical) promotion of cell reaction, metallic catalyst
The uniform compound and effective dispersion of (such as cobalt base oxide) and carbon material is a current master for preparing positive nanocomposite
Problem is wanted, and the evenly dispersed of metallic element allows its metal oxide catalyst after carbonization, activation uniformly to divide in MOF
It dissipates, being prepared by hollow MOF has three-dimensional N doping porous carbon@cobalt-base catalyst nanocages composite materials, can be mixed by nitrogen
Synergistic effect between miscellaneous carbon material, metal oxide and nanometer basket structure, promotes the performance of lithium-air battery.
The present invention is described in further detail with reference to embodiment：
Embodiment 1
The 2-methylimidazole and cobalt nitrate that quality is 50mg are weighed respectively, are dissolved in methanol respectively, are made its concentration be
20mmol/L.2-methylimidazole solution is added drop-wise to 100mL/min rates in Cobalt salts solution, life in 12 hours is then allowed to stand
At block MOF, products therefrom is centrifuged, 60 DEG C of dryings of vacuum after being used in combination ethyl alcohol to wash repeatedly.50mg blocks MOF is weighed to put
Enter in 60mmol/L cobalt nitrates/zinc methanol solution, wherein the mass ratio of Cobalt salts and metal zinc salt is 10：90, block MOF exists
A concentration of 10mg/mL in mixed solution, 100 DEG C of 6 hours reaction time.Then products therefrom is centrifuged, second is used in combination
60 DEG C of dryings of vacuum, obtain hollow MOF after alcohol washs repeatedly.Then 800 DEG C of carbonization times 6 hours under a nitrogen.Finally in sky
Lower 300 DEG C of gas activates 4 hours, obtains three-dimensional N doping porous carbon@Co3O4Nanocages composite material.
Material specific surface area prepared by embodiment 1 is 2000m2g-1, composite material is coated to foam with PVDF bonding agents
Air cathode is prepared on nickel and is assembled into lithium-air battery, and battery discharge specific capacity is 15000mA h g under pure oxygen atmosphere-1,
Capacity retention ratio is up to 85% after cycle 30 times.
Embodiment 2
The 2-methylimidazole and cobalt nitrate that quality is 50mg are weighed respectively, are dissolved in methanol respectively, are made its concentration be
80mmol/L.2-methylimidazole solution is added drop-wise to 5mL/min rates in Cobalt salts solution, is then allowed to stand 24 hours and generates
Block MOF, products therefrom is centrifuged, 60 DEG C of dryings of vacuum after being used in combination ethyl alcohol to wash repeatedly.30mg blocks MOF is weighed to be put into
In 80mmol/L cobalt nitrates/zinc methanol solution, wherein the mass ratio of Cobalt salts and metal zinc salt is 90：10, block MOF are mixed
A concentration of 90mg/mL in solution is closed, 100 DEG C of 6 hours reaction time.Then products therefrom is centrifuged, ethyl alcohol is used in combination
60 DEG C of dryings of vacuum after washing repeatedly, obtain hollow MOF.Then 600 DEG C of carbonization times 6 hours under a nitrogen.Finally in air
Lower 300 DEG C activate 4 hours, obtain three-dimensional N doping porous carbon@Co3O4Nanocages composite material.
Material specific surface area prepared by embodiment 2 is 2200m2g-1, composite material is coated to foam with PVDF bonding agents
Air cathode is prepared on nickel and is assembled into lithium-air battery, and battery discharge specific capacity is 17000mA h g under pure oxygen atmosphere-1,
Capacity retention ratio is up to 80% after cycle 50 times.
Embodiment 3
The 2-methylimidazole and cobalt chloride that quality is 50mg are weighed respectively, are dissolved in methanol respectively, are made its concentration be
40mmol/L.2-methylimidazole solution is added drop-wise to 30mL/min rates in Cobalt salts solution, is then allowed to stand 1 hour and generates
Block MOF, products therefrom is centrifuged, 60 DEG C of dryings of vacuum after being used in combination ethyl alcohol to wash repeatedly.20mg blocks MOF is weighed to be put into
In 20mmol/L cobalt chlorides/zinc ethanol solution, wherein the mass ratio of Cobalt salts and metal zinc salt is 50：50, block MOF are mixed
A concentration of 60mg/mL in solution is closed, 100 DEG C of 6 hours reaction time.Then products therefrom is centrifuged, ethyl alcohol is used in combination
60 DEG C of dryings of vacuum after washing repeatedly, obtain hollow MOF.Then 1000 DEG C of carbonization times 1 hour under a nitrogen.Finally in air
Lower 300 DEG C activate 4 hours, obtain three-dimensional N doping porous carbon@Co3O4Nanocages composite material.
Material specific surface area prepared by embodiment 3 is 1900m2g-1, composite material is coated to foam with PVDF bonding agents
Air cathode is prepared on nickel and is assembled into lithium-air battery, and battery discharge specific capacity is 14000mA h g under pure oxygen atmosphere-1,
Capacity retention ratio is up to 85% after cycle 50 times.
Embodiment 4
The 2-methylimidazole and cobaltous sulfate that quality is 50mg are weighed respectively, are dissolved in methanol respectively, are made its concentration be
60mmol/L.2-methylimidazole solution is added drop-wise to 70mL/min rates in Cobalt salts solution, life in 12 hours is then allowed to stand
At block MOF, products therefrom is centrifuged, 60 DEG C of dryings of vacuum after being used in combination ethyl alcohol to wash repeatedly.40mg blocks MOF is weighed to put
Enter in 60mmol/L cobaltous sulfates/zinc aqueous solution, wherein the mass ratio of Cobalt salts and metal zinc salt is 40：90, block MOF are mixed
A concentration of 50mg/mL in solution is closed, 100 DEG C of 6 hours reaction time.Then products therefrom is centrifuged, ethyl alcohol is used in combination
60 DEG C of dryings of vacuum after washing repeatedly, obtain hollow MOF.Then 800 DEG C of carbonization times 4 hours under a nitrogen.Finally in air
Lower 300 DEG C activate 4 hours, obtain three-dimensional N doping porous carbon@Co3O4Nanocages composite material.
Material specific surface area prepared by embodiment 4 is 2000m2g-1, composite material is coated to foam with PVDF bonding agents
Air cathode is prepared on nickel and is assembled into lithium-air battery, and battery discharge specific capacity is 18000mA h g under pure oxygen atmosphere-1,
Capacity retention ratio is up to 70% after cycle 100 times.
Embodiment 5
The 2-methylimidazole and cobalt chloride that quality is 50mg are weighed respectively, are dissolved in methanol respectively, are made its concentration be
40mmol/L.2-methylimidazole solution is added drop-wise to 30mL/min rates in Cobalt salts solution, life in 12 hours is then allowed to stand
At block MOF, products therefrom is centrifuged, 60 DEG C of dryings of vacuum after being used in combination ethyl alcohol to wash repeatedly.20mg blocks MOF is weighed to put
Enter in 80mmol/L cobalt chlorides/zinc ethanol solution, wherein the mass ratio of Cobalt salts and metal zinc salt is 50：50, block MOF exists
A concentration of 70mg/mL in mixed solution, 60 DEG C of 12 hours reaction time.Then products therefrom is centrifuged, second is used in combination
60 DEG C of dryings of vacuum, obtain hollow MOF after alcohol washs repeatedly.Then 700 DEG C of carbonization times 4 hours under a nitrogen.Finally in sky
Lower 400 DEG C of gas activates 6 hours, obtains three-dimensional N doping porous carbon@Co3O4Nanocages composite material.
Material specific surface area prepared by embodiment 5 is 2100m2g-1, composite material is coated to foam with PVDF bonding agents
Air cathode is prepared on nickel and is assembled into lithium-air battery, and battery discharge specific capacity is 13000mA h g under pure oxygen atmosphere-1,
Capacity retention ratio is up to 80% after cycle 100 times.
Embodiment 6
The 2-methylimidazole and cobalt chloride that quality is 50mg are weighed respectively, are dissolved in methanol respectively, are made its concentration be
40mmol/L.2-methylimidazole solution is added drop-wise to 30mL/min rates in Cobalt salts solution, life in 12 hours is then allowed to stand
At block MOF, products therefrom is centrifuged, 60 DEG C of dryings of vacuum after being used in combination ethyl alcohol to wash repeatedly.20mg blocks MOF is weighed to put
Enter in 40mmol/L cobalt chlorides/zinc ethanol solution, wherein the mass ratio of Cobalt salts and metal zinc salt is 50：50, block MOF exists
A concentration of 40mg/mL in mixed solution, 150 DEG C of 1 hour reaction time.Then products therefrom is centrifuged, second is used in combination
60 DEG C of dryings of vacuum, obtain hollow MOF after alcohol washs repeatedly.Then 900 DEG C of carbonization times 3 hours under a nitrogen.Finally in sky
Lower 30 DEG C of gas activates 4 hours, obtains three-dimensional N doping porous carbon@CoO nanocages composite materials.
Material specific surface area prepared by embodiment 6 is 2000m2g-1, composite material is coated to foam with PVDF bonding agents
Air cathode is prepared on nickel and is assembled into lithium-air battery, and battery discharge specific capacity is 10000mA h g under pure oxygen atmosphere-1,
Capacity retention ratio is up to 75% after cycle 50 times.
Claims (10)
1. a kind of preparation method of lithium-oxygen battery N doping porous carbon@cobalt-base catalyst nanocages composite materials, which is characterized in that
Include the following steps：
(1) 2-methylimidazole and Cobalt salts are weighed, is dissolved in solvent respectively, 2-methylimidazole solution is obtained and Cobalt salts is molten
Liquid；
(2) 2-methylimidazole solution is added drop-wise in Cobalt salts solution, or by 2-methylimidazole solution and Cobalt salts solution
It is added drop-wise in alcohol solvent at the same rate, is then allowed to stand hatching, products therefrom is centrifuged, ethyl alcohol is used in combination to wash repeatedly
After be dried to obtain block MOF；
(3) block MOF is put into the mixed solution of Cobalt salts and metal zinc salt, it is small that 1-12 is reacted at a temperature of 60-150 DEG C
When, then products therefrom is centrifuged, hollow MOF is dried to obtain after being used in combination ethyl alcohol to wash repeatedly；
(4) the hollow MOF of preparation is carbonized under an inert atmosphere；
(5) powder obtained after carbonization is activated in air atmosphere to get to lithium-oxygen battery N doping porous carbon@cobalt-baseds
Catalyst nano cage composite material.
2. a kind of lithium-oxygen battery N doping porous carbon@cobalt-base catalyst nanocages composite materials according to claim 1
Preparation method, which is characterized in that the concentration of 2-methylimidazole solution and Cobalt salts solution is 20-80mmol/ in step (1)
L。
3. a kind of lithium-oxygen battery N doping porous carbon@cobalt-base catalyst nanocages composite materials according to claim 1
Preparation method, which is characterized in that Cobalt salts are nitric acid cobalt salt, chlorination cobalt salt or sulfuric acid cobalt salt in step (1)；In step (1)
Solvent is the mixed solution of methanol, ethyl alcohol, water or water and methanol or ethyl alcohol.
4. a kind of lithium-oxygen battery N doping porous carbon@cobalt-base catalyst nanocages composite materials according to claim 1
Preparation method, which is characterized in that the mass ratio of 2-methylimidazole and Cobalt salts is 1 in step (2):1, and drop in step (2)
Rate of acceleration is 5~100mL/min.
5. a kind of lithium-oxygen battery N doping porous carbon@cobalt-base catalyst nanocages composite materials according to claim 1
Preparation method, which is characterized in that time of repose is 1-24 hours in step (2).
6. a kind of lithium-oxygen battery N doping porous carbon@cobalt-base catalyst nanocages composite materials according to claim 1
Preparation method, which is characterized in that Cobalt salts and metallic zinc mixed salt solution are by Cobalt salts and metal zinc salt in step (3)
It dissolves in solvent to obtain, wherein the mass ratio of Cobalt salts and metal zinc salt is (10-90)：(90-10).
7. a kind of lithium-oxygen battery N doping porous carbon@cobalt-base catalyst nanocages composite materials according to claim 6
Preparation method, which is characterized in that Cobalt salts are nitric acid cobalt salt, chlorination cobalt salt or sulfuric acid cobalt salt in step (3), and metal zinc salt is
Nitric acid zinc salt, chlorination zinc salt or sulfuric acid zinc salt, solvent are the mixed solution of methanol, ethyl alcohol, water or water and methanol or ethyl alcohol.
8. a kind of lithium-oxygen battery N doping porous carbon@cobalt-base catalyst nanocages composite materials according to claim 1
Preparation method, which is characterized in that it is molten mixing to be added in block MOF by a concentration of 20-80mmol/L of mixed solution in step (3)
After in liquid, a concentration of 10-90mg/mL of block MOF.
9. a kind of lithium-oxygen battery N doping porous carbon@cobalt-base catalyst nanocages composite materials according to claim 1
Preparation method, which is characterized in that carburizing temperature is 600-1000 DEG C in step (4), and carbonization time is 1-6 hours.
10. a kind of lithium-oxygen battery N doping porous carbon@cobalt-base catalyst nanocages composite materials according to claim 1
Preparation method, which is characterized in that activation temperature is 30-400 DEG C in step (5), and soak time is 1-6 hours.
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| CN114797933B (en) * | 2022-03-31 | 2023-06-13 | 南京工业大学 | Nano-cage composite catalyst and preparation method and application thereof |
| CN114883585A (en) * | 2022-04-21 | 2022-08-09 | 同济大学 | Multifunctional non-noble metal nitrogen-doped carbon catalyst and preparation method and application thereof |
| CN115411276A (en) * | 2022-09-20 | 2022-11-29 | 陕西科技大学 | Preparation method of core-shell nano cage electrocatalyst for oxygen reduction reaction |
| CN115411276B (en) * | 2022-09-20 | 2023-10-20 | 陕西科技大学 | Preparation method of core-shell nano-cage electrocatalyst for oxygen reduction reaction |
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