CN115425237A - Lithium-oxygen battery bimetal organic frame anode catalyst and preparation method thereof - Google Patents
Lithium-oxygen battery bimetal organic frame anode catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN115425237A CN115425237A CN202210974205.4A CN202210974205A CN115425237A CN 115425237 A CN115425237 A CN 115425237A CN 202210974205 A CN202210974205 A CN 202210974205A CN 115425237 A CN115425237 A CN 115425237A
- Authority
- CN
- China
- Prior art keywords
- lithium
- solution
- oxygen battery
- catalyst
- htp
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- QTJOIXXDCCFVFV-UHFFFAOYSA-N [Li].[O] Chemical compound [Li].[O] QTJOIXXDCCFVFV-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000002070 nanowire Substances 0.000 claims abstract description 13
- 238000005341 cation exchange Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 239000013384 organic framework Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 238000007789 sealing Methods 0.000 claims description 10
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 9
- 229910052707 ruthenium Inorganic materials 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- FXVCQLLAIUUIHJ-UHFFFAOYSA-N triphenylene-2,3,6,7,10,11-hexamine Chemical group C12=CC(N)=C(N)C=C2C2=CC(N)=C(N)C=C2C2=C1C=C(N)C(N)=C2 FXVCQLLAIUUIHJ-UHFFFAOYSA-N 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 239000012621 metal-organic framework Substances 0.000 claims description 7
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 5
- 239000013110 organic ligand Substances 0.000 claims description 5
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000012459 cleaning agent Substances 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical compound [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 claims description 2
- 239000006260 foam Substances 0.000 claims 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000007599 discharging Methods 0.000 abstract description 4
- 230000004888 barrier function Effects 0.000 abstract description 2
- 239000013099 nickel-based metal-organic framework Substances 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
- H01M8/0273—Sealing or supporting means around electrodes, matrices or membranes with sealing or supporting means in the form of a frame
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Materials Engineering (AREA)
- Hybrid Cells (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a bimetallic organic frame anode catalyst of a lithium-oxygen battery and a preparation method thereof, belonging to the technical field of lithium-oxygen batteries. Aiming at the problems of high charge-discharge overvoltage, low energy efficiency and the like caused by high anode reaction energy barrier of the conventional lithium-oxygen battery, the Ru atoms are anchored on a Ni-based metal organic framework (Ni-HTP) by using a simple cation exchange method to obtain the bimetallic NiRu-HTP anode catalyst. The catalyst has the advantages of nanowire array structure, uniform size, high specific surface area, stable structure, high catalytic activity and the like, effectively improves the reaction kinetics of the anode, and reduces the charging and discharging overvoltage of the lithium-oxygen battery.
Description
Technical Field
The invention belongs to the field of lithium-oxygen batteries, and particularly relates to a preparation method of a bimetallic organic frame anode catalyst of a lithium-oxygen battery.
Background
The lithium-oxygen battery has an ultra-high theoretical energy density (3600 Wh kg) -1 ) The method is an energy storage technology with development potential. The working principle is based on a reversible reaction
The theoretical equilibrium voltage is 2.96V. However, the higher reaction energy barrier of the positive electrode results in large polarization and low energy efficiency in the charge and discharge processes. Noble metals, metal oxides and carbon materials have been used as positive electrode catalysts for lithium-oxygen batteries to promote their reaction kinetics. Among them, noble metals and their alloys exhibit excellent catalytic activity, but are expensive and have low selectivity, limiting their application in lithium-oxygen batteries. The metal oxide has the advantages of abundant reserves, low price and the like, but the active site of the metal oxide is easy to change in the reaction process, and the stability is poor. The carbon material has a complex preparation process and insufficient catalytic active sites, so that the charging and discharging overvoltage of the lithium-oxygen battery is always larger than 1V. The development of highly efficient and stable catalysts to accelerate the kinetics of the positive electrode reaction is the key to the development of lithium-oxygen batteries.
Metal-Organic Frameworks (MOFs) are a class of porous materials formed by coordination of Metal nodes and Organic ligands, have the advantages of high specific surface area, high dispersion of catalytic active centers, stable structure and the like, are used as high-efficiency anode catalysts of lithium-oxygen batteries, and provide high discharge capacity and moderate reaction kinetics. In addition, the reasonable design and synthesis of the MOFs catalyst can adjust the electronic structure of the metal node, accelerate electron transfer and further improve the reaction kinetics of the anode.
Disclosure of Invention
The invention aims to solve the problems of high charging and discharging overvoltage, low energy efficiency and the like caused by slow reaction kinetics of a lithium-oxygen battery anode, and provides a preparation method of a high-efficiency bimetal organic framework anode catalyst of a lithium-oxygen battery.
The technical scheme of the invention is as follows:
a lithium-oxygen battery bimetal organic frame anode catalyst utilizes a cation exchange method to synthesize a NiRu-HTP nanowire anode catalyst on carbon paper in situ, and the preparation method comprises the following steps:
adding the nickel source solution into 2,3,6,7,10, 11-hexa-amino triphenylene organic ligand aqueous solution, and adding ammonia water to obtain a first solution for later use; putting the carbon paper into the first solution, sealing, heating, naturally cooling, washing the obtained electrode, and drying in vacuum to obtain a Ni-HTP electrode; and dispersing a ruthenium source in an ethanol solution to prepare a dark brown solution II, putting the prepared Ni-HTP electrode into the solution II, sealing, heating, naturally cooling, washing the obtained electrode, and drying in vacuum to obtain the NiRu-HTP anode catalyst, namely the bimetallic organic framework anode catalyst of the lithium-oxygen battery.
A preparation method of a simple, efficient and stable lithium-oxygen battery bimetal organic framework anode catalyst utilizes a cation exchange method to synthesize bimetal organic framework nanowires, namely a NiRu-HTP anode catalyst, in situ on carbon paper, and comprises the following steps:
(1) Dissolving 2,3,6,7,10, 11-hexa-amino triphenylene organic ligand in deionized water, and performing ultrasonic treatment for several minutes to prepare a light yellow transparent solution.
(2) Dispersing a nickel source in deionized water, and uniformly stirring to prepare a colorless transparent solution.
(3) Slowly pouring the nickel source solution obtained in the step (2) into the solution obtained in the step (1) under the action of magnetic stirring, continuously stirring for a period of time to obtain a blue solution, and dropwise adding a plurality of drops of ammonia water solution.
(4) And (4) putting the cut carbon paper into the solution obtained in the step (3), sealing and putting the carbon paper into an oven to be heated for a plurality of hours. And naturally cooling to room temperature, washing the obtained electrode, and drying in vacuum to obtain the Ni-HTP electrode.
(5) Dispersing a ruthenium source in an ethanol solution, and uniformly stirring to prepare a dark brown solution.
(6) And (4) placing the electrode obtained in the step (4) into the solution obtained in the step (5), sealing and placing in an oven to heat for a plurality of hours. And naturally cooling to room temperature, washing the obtained electrode, and drying in vacuum to obtain the NiRu-HTP electrode.
Preferably, in step (1), the concentration of the 2,3,6,7,10, 11-hexaaminotriphenylene solution is 8mmol L -1 。
Preferably, in the step (2), the nickel source is nickel acetate, nickel chloride and nitric acidOne kind of nickel with a concentration of 12mmol L -1 。
Preferably, in the step (3), the concentration of the ammonia water is 14mol L -1 The stirring time is 5 to 10 minutes.
Preferably, in the step (4), the current collector is one of carbon paper, carbon cloth or foamed nickel, the heating temperature is 50-70 ℃, the reaction time is 4-12 hours, the cleaning agent for washing is deionized water and ethanol, and the vacuum drying condition is 60-80 ℃ for heating 10-12 hours.
Preferably, in the step (5), the ruthenium source is one of ruthenium chloride, ruthenium acetylacetonate and ruthenium nitrate, and the concentration is 25mmol L -1 . In the step (5), ferric chloride can be used for replacing a ruthenium source, and other processes are unchanged, so that the NiFe-HTP nanowire is finally prepared and used as a positive electrode catalyst.
Preferably, in the step (6), the heating temperature is 60-80 ℃, the reaction time is 10-12 hours, the cleaning agent for washing is deionized water and ethanol, and the vacuum drying condition is 60-80 ℃ for heating 10-12 hours.
The application method of the bimetallic organic framework catalyst of the lithium-oxygen battery is used as the anode catalyst of the lithium-oxygen battery.
The invention has the advantages and beneficial effects that:
the NiRu-HTP catalyst prepared by the method has the advantages of nano array structure, small size, large specific surface area, high catalytic activity, stable chemical property and the like.
The preparation method used in the invention can be extended to the preparation of other bimetallic organic framework catalysts, such as NiFe-HTP, niCo-HTP, niMn-HTP and the like.
The NiRu-HTP catalyst prepared by the invention shows lower charge-discharge overvoltage in a lithium-oxygen battery.
Drawings
FIG. 1 is an XRD pattern of Ni-HTP and NiRu-HTP powders obtained in example 1;
FIG. 2 is an SEM image of the NiRu-HTP nanowires obtained in example 1;
FIG. 3 shows the discharge current of the NiRu-HTP nanowire obtained in example 1 under different current densitiesPressure-volume diagram (electrolyte: 1M lithium bis (trifluoromethane) sulfonimide (LiTFSI) dissolved in tetraglyme (G4), addition amount is 60.0L, positive active material loading is 0.3mg cm -2 (ii) a The effective area is 0.785cm 2 )；
FIG. 4 shows the assembly of the NiFe-HTP catalyst obtained in example 2 into a lithium-oxygen cell at 200mA g -1 Discharge voltage-capacity diagram under current density (electrolyte: 1M LiTFSI in G4; positive electrode active material loading: 0.3mg cm) -2 (ii) a The effective area is 0.785cm 2 )。
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings.
The purity of 2,3,6,7,10, 11-hexa-amino-triphenylene, nickel chloride and ruthenium chloride used in the examples was higher than 97%.
Example 1:
the preparation method of the bimetallic organic frame anode catalyst for the lithium-oxygen battery in the embodiment comprises the following steps:
(1) 21.5mg of 2,3,6,7,10, 11-hexaaminotriphenylene was weighed and dispersed in 4mL of deionized water and sonicated for several minutes to dissolve completely.
(2) 14.2mg of nickel chloride was weighed, dissolved in 4mL of deionized water, and dispersed uniformly under magnetic stirring.
(3) Slowly pouring the nickel chloride solution obtained in the step (2) into the solution obtained in the step (1) under the action of magnetic stirring, continuously stirring for a period of time to obtain a blue solution, and dropwise adding 0.8mL of ammonia water solution.
(4) And (4) putting the cut carbon paper into the solution obtained in the step (3), sealing, putting the carbon paper into an oven, heating to 65 ℃ and preserving heat for 4 hours. After naturally cooling to room temperature, the obtained electrode was washed several times with deionized water and ethanol and vacuum-dried.
(5) 80mg of ruthenium chloride is weighed and dispersed in 20mL of ethanol solution, and the mixture is stirred uniformly to prepare dark brown solution.
(6) And (5) putting the electrode obtained in the step (4) into the solution obtained in the step (5), sealing, putting into an oven, heating to 70 ℃, and keeping the temperature for 10 hours. And naturally cooling to room temperature, washing the obtained electrode with deionized water and ethanol for several times, and drying in vacuum to obtain the NiRu-HTP catalyst.
Figure 1 is the XRD pattern of the catalyst obtained in example 1: FIG. 1 shows that the successfully prepared NiRu-HTP catalyst is successfully prepared and has good crystallinity.
FIG. 2 is an SEM image of the catalyst obtained in example 1, and FIG. 2 can obtain the micro-morphology of the NiRu-HTP catalyst which is a nanowire array structure with the diameter of about 30nm.
The NiRu-HTP nanowire prepared by the method is used as a positive electrode catalyst, a lithium plate is used as a negative electrode, 1M LiTFSI in G4 is used as electrolyte, the NiRu-HTP nanowire is assembled into a lithium-oxygen battery, and the discharge performance of the lithium-oxygen battery under different current densities is tested under the condition of room temperature (25 ℃), as shown in figure 3, the current densities are 200mAg, 500 mAg and 1000mAg -1 The discharge voltage is 2.75V, 2.73V and 2.69V, and the charge voltage is 3.51V, 3.62V and 3.72V.
Example 2:
the preparation method of the lithium-oxygen battery bimetallic organic framework cathode catalyst in the embodiment is carried out according to the step of the embodiment 1.
Different from the example 1, in the step (2), ruthenium chloride is replaced by ferric chloride, other processes are not changed, the NiFe-HTP nanowire is finally prepared and used as a positive electrode catalyst, a lithium sheet is used as a negative electrode, and the NiFe-HTP nanowire is assembled into a lithium-oxygen battery by 1M LiTFSI in G4, the charging and discharging curve of the lithium-oxygen battery is tested under the condition of room temperature (25 ℃) and is shown in figure 4, and the current density is 200mAg -1 The discharge voltage was 2.71V and the charge voltage was 3.73V.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily think of the changes or substitutions within the technical scope of the present invention, and shall cover the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A lithium-oxygen battery bimetal organic frame anode catalyst is characterized in that: the NiRu-HTP nanowire anode catalyst is synthesized in situ on carbon paper by a cation exchange method, and the preparation method comprises the following steps:
adding the nickel source solution into a 2,3,6,7,10, 11-hexaamino triphenylene organic ligand aqueous solution, and adding ammonia water to obtain a first solution for later use; putting the carbon paper into the first solution, sealing, heating, naturally cooling, washing the obtained electrode, and drying in vacuum to obtain a Ni-HTP electrode; and dispersing a ruthenium source in an ethanol solution to prepare a dark brown solution II, putting the prepared Ni-HTP electrode into the solution II, sealing, heating, naturally cooling, washing the obtained electrode, and drying in vacuum to obtain the NiRu-HTP anode catalyst, namely the bimetallic organic framework anode catalyst of the lithium-oxygen battery.
2. The preparation method of the bimetallic organic framework anode catalyst of the lithium-oxygen battery as claimed in claim 1 is characterized by comprising the following specific steps:
(1) Dissolving 2,3,6,7,10, 11-hexa-amino triphenylene organic ligand in deionized water, and dissolving by ultrasonic to prepare light yellow transparent solution;
(2) Dispersing a nickel source in deionized water, and uniformly stirring to prepare a colorless transparent solution;
(3) Slowly pouring the nickel source solution obtained in the step (2) into the solution obtained in the step (1) under the action of magnetic stirring, continuously stirring for a period of time to obtain a blue solution, and dropwise adding a plurality of drops of ammonia water solution;
(4) Putting the cut carbon paper into the solution obtained in the step (3), sealing and putting the carbon paper into an oven for heating, naturally cooling to room temperature, washing the obtained electrode and drying in vacuum to obtain a Ni-HTP electrode;
(5) Dispersing a ruthenium source in an ethanol solution, and uniformly stirring to prepare a dark brown solution;
(6) And (3) putting the electrode obtained in the step (4) into the solution obtained in the step (5), sealing and putting into an oven for heating, naturally cooling to room temperature, washing and vacuum drying the obtained electrode to obtain the NiRu-HTP positive electrode catalyst, namely the lithium-oxygen battery bimetal organic frame positive electrode catalyst.
3. According to claim2, the preparation method of the lithium-oxygen battery bimetal organic framework anode catalyst is characterized in that the concentration of the 2,3,6,7,10, 11-hexa-amino triphenylene solution prepared in the step (1) is 8mmol L -1 。
4. The method for preparing the bi-metal organic framework cathode catalyst of the lithium-oxygen battery as claimed in claim 2, wherein the nickel source in the step (2) is one of nickel acetate, nickel chloride and nickel nitrate, and the concentration is 12mmol L -1 。
5. The method for preparing the bi-metal organic framework positive electrode catalyst of the lithium-oxygen battery as claimed in claim 2, wherein the ammonia water concentration in the step (3) is 14mol L -1 The stirring time is 5 to 10 minutes.
6. The preparation method of the lithium-oxygen battery bimetal organic frame anode catalyst as claimed in claim 2, wherein the current collector in the step (4) is one of carbon paper, carbon cloth or foam nickel, the heating temperature is 50-70 ℃, the reaction time is 4-12 hours, the cleaning agent for washing is deionized water and ethanol, and the vacuum drying condition is 60-80 ℃ and the heating time is 10-12 hours.
7. The method for preparing the bi-metal organic framework cathode catalyst of the lithium-oxygen battery as claimed in claim 2, wherein the ruthenium source in the step (5) is one of ruthenium chloride, ruthenium acetylacetonate or ruthenium nitrate, and the concentration of the ruthenium source is 25mmol L -1 。
8. The method for preparing the bi-metal organic framework positive electrode catalyst of the lithium-oxygen battery as claimed in claim 6, wherein in the step (5), the ruthenium source is replaced by ferric chloride, and other processes are not changed, so that the NiFe-HTP nanowires are finally prepared and used as the positive electrode catalyst.
9. The preparation method of the bimetallic organic frame anode catalyst of the lithium-oxygen battery as claimed in claim 2, wherein the heating temperature in the step (4) is 60-80 ℃, the reaction time is 10-12 hours, the cleaning agent for washing is deionized water and ethanol, the vacuum drying condition is 60-80 ℃, and the heating time is 10-12 hours.
10. The application method of the bimetallic organic framework catalyst of the lithium-oxygen battery as claimed in claim 1, characterized by being used as a positive electrode catalyst of the lithium-oxygen battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210974205.4A CN115425237A (en) | 2022-08-15 | 2022-08-15 | Lithium-oxygen battery bimetal organic frame anode catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210974205.4A CN115425237A (en) | 2022-08-15 | 2022-08-15 | Lithium-oxygen battery bimetal organic frame anode catalyst and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115425237A true CN115425237A (en) | 2022-12-02 |
Family
ID=84198942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210974205.4A Pending CN115425237A (en) | 2022-08-15 | 2022-08-15 | Lithium-oxygen battery bimetal organic frame anode catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115425237A (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104466203A (en) * | 2013-09-22 | 2015-03-25 | 中国科学院上海硅酸盐研究所 | Composite catalyst of air electrode of lithium-air cell |
| CN108754531A (en) * | 2018-05-29 | 2018-11-06 | 浙江大学 | A kind of preparation method of the nano combined electrocatalysis material containing Co and Ru bimetallic carbon |
| CN109148902A (en) * | 2017-06-13 | 2019-01-04 | 西安绿行户外运动有限公司 | To the bifunctional catalyst of lithium-air battery |
| CN109833914A (en) * | 2019-03-20 | 2019-06-04 | 河北工业大学 | A kind of palladium catalyst and its preparation method and application of Cu Base Metal organic frame load |
| CN111554936A (en) * | 2020-05-18 | 2020-08-18 | 齐鲁工业大学 | Conductive MOF modified carbon fiber paper insertion layer material for lithium-sulfur battery |
| CN111574722A (en) * | 2019-02-19 | 2020-08-25 | 中国科学院福建物质结构研究所 | Photoconductive metal organic framework thin film material, preparation method and application thereof |
| CN112981429A (en) * | 2021-02-24 | 2021-06-18 | 江南大学 | Metal organic framework and hydroxide heterojunction electrocatalyst and in-situ preparation method and application thereof |
| CN113937274A (en) * | 2021-11-22 | 2022-01-14 | 江苏科技大学 | Metal organic framework composite material and preparation method and application thereof |
| KR20220032303A (en) * | 2020-09-07 | 2022-03-15 | 한국에너지기술연구원 | Method for manufacturing metal-organic framework, metal-organic framework, electrode, catalyst and absorbent comprising same |
| CN114768878A (en) * | 2022-05-07 | 2022-07-22 | 中国科学技术大学 | Preparation method of bimetallic conductive MOF catalyst |
-
2022
- 2022-08-15 CN CN202210974205.4A patent/CN115425237A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104466203A (en) * | 2013-09-22 | 2015-03-25 | 中国科学院上海硅酸盐研究所 | Composite catalyst of air electrode of lithium-air cell |
| CN109148902A (en) * | 2017-06-13 | 2019-01-04 | 西安绿行户外运动有限公司 | To the bifunctional catalyst of lithium-air battery |
| CN108754531A (en) * | 2018-05-29 | 2018-11-06 | 浙江大学 | A kind of preparation method of the nano combined electrocatalysis material containing Co and Ru bimetallic carbon |
| CN111574722A (en) * | 2019-02-19 | 2020-08-25 | 中国科学院福建物质结构研究所 | Photoconductive metal organic framework thin film material, preparation method and application thereof |
| CN109833914A (en) * | 2019-03-20 | 2019-06-04 | 河北工业大学 | A kind of palladium catalyst and its preparation method and application of Cu Base Metal organic frame load |
| CN111554936A (en) * | 2020-05-18 | 2020-08-18 | 齐鲁工业大学 | Conductive MOF modified carbon fiber paper insertion layer material for lithium-sulfur battery |
| KR20220032303A (en) * | 2020-09-07 | 2022-03-15 | 한국에너지기술연구원 | Method for manufacturing metal-organic framework, metal-organic framework, electrode, catalyst and absorbent comprising same |
| CN112981429A (en) * | 2021-02-24 | 2021-06-18 | 江南大学 | Metal organic framework and hydroxide heterojunction electrocatalyst and in-situ preparation method and application thereof |
| CN113937274A (en) * | 2021-11-22 | 2022-01-14 | 江苏科技大学 | Metal organic framework composite material and preparation method and application thereof |
| CN114768878A (en) * | 2022-05-07 | 2022-07-22 | 中国科学技术大学 | Preparation method of bimetallic conductive MOF catalyst |
Non-Patent Citations (1)
| Title |
|---|
| ELISE M. MINER等: ""Electrochemical oxygen reduction catalysed by Ni3(hexaiminotriphenylene)2"", 《NATURE COMMUNICATIONS》, vol. 7, 8 March 2016 (2016-03-08), pages 10942 - 10948 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110380062B (en) | Preparation method of sulfur-doped bifunctional oxygen catalyst based on ZIF-67 and conductive graphene | |
| Tian et al. | In-situ cobalt-nickel alloy catalyzed nitrogen-doped carbon nanotube arrays as superior freestanding air electrodes for flexible zinc-air and aluminum-air batteries | |
| CN111001427B (en) | Cobalt-nitrogen co-doped carbon-based electrocatalyst material and preparation method thereof | |
| CN108923051A (en) | A kind of nitrogen-doped carbon nanometer pipe composite catalyst of package metals cobalt nano-particle and its application | |
| CN108365230A (en) | A kind of universality preparation method and application for the air electrode that active site is combined with electrode structure | |
| CN111001428B (en) | Metal-free carbon-based electrocatalyst, preparation method and application | |
| CN111921560B (en) | Lattice-distorted ultrathin metal organic framework nanosheet catalyst, and preparation method and application thereof | |
| CN110611105B (en) | Preparation method of ORR catalyst | |
| CN113745549B (en) | Preparation method of Mn monoatomic supported N-doped carbon polyhedral catalyst | |
| CN111933961B (en) | Binary CoFe alloy loaded g-C3N4Catalyst and preparation method thereof | |
| CN114628696B (en) | Preparation method of porous carbon-supported cobalt-based bifunctional oxygen catalyst | |
| CN110721749A (en) | NiCo coated with metal organic framework structure derived carbon composite2S4Nanowire array-shaped electrocatalyst and preparation method thereof | |
| Zhou et al. | Graphitic-nitrogen-enriched carbon skeleton with embedment of Fe3C for superior performance air cathode in zinc-air battery | |
| CN113967483A (en) | Application of bimetallic two-dimensional MOF series catalyst to lithium-sulfur battery | |
| CN110148763B (en) | Preparation method and application of Fe-doped Mn3O4 carbon-nitrogen material with hollow nano-framework structure | |
| CN115425237A (en) | Lithium-oxygen battery bimetal organic frame anode catalyst and preparation method thereof | |
| CN113471457B (en) | Preparation and application of cationic MOFs derivative catalyst | |
| CN115241577A (en) | Transition metal-nitrogen/sulfur/selenium doped porous carbon catalyst and neutral zinc-air battery | |
| CN114709428A (en) | Defect tungsten oxide/ruthenium nanoparticle composite catalyst and preparation method and application thereof | |
| CN113594474A (en) | Preparation method and application of self-catalytic growth Zn/Co-N-C carbon nanotube oxygen reduction catalyst | |
| CN113921834A (en) | Preparation and application of self-supporting MOF-derived carbon-coated cobalt selenide nano material | |
| CN112537806A (en) | Preparation method of nickel and manganese double-metal fluoride cathode catalyst of lithium air battery | |
| Wang et al. | Metallic cobalt encapsulated in N-doped carbon nanowires: a highly active bifunctional catalyst for oxygen reduction and evolution | |
| CN114759194B (en) | Manganese-based ternary integrated difunctional oxygen electrode and preparation method and application thereof | |
| CN115747876A (en) | Preparation method and application of Pt particle-loaded two-dimensional iron-based metal organic framework nano array |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |