CN111682208A - Composite organic frame nano electrode material and preparation method thereof - Google Patents
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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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a composite organic frame nano electrode material and a preparation method thereof, which can prepare a molecular level hybridized composite organic frame nano electrode material with coordination effect. The composite organic framework nano electrode material not only has an adjustable flower-ball-shaped microstructure, but also can activate the lithium storage performance of a metal manganese center and C-C in a conjugated benzene ring in the composite material. Meanwhile, the preparation process of the composite material has short reaction time, low requirement on equipment and good prospect.
Description
Technical Field
The invention relates to a lithium ion battery electrode material and a preparation method thereof, in particular to a porous framework nano electrode material and a preparation method thereof, belonging to the technical field of preparation of lithium ion power battery electrode materials.
Background
At present, lithium ion batteries in novel electric vehicles have wide application. Graphite is an important negative electrode material in most commercial lithium ion batteries. However, the low theoretical specific capacity limits its wide application in energy storage devices. Currently, the most important work on clean energy is devoted to the development of novel electrode materials with high specific capacity, excellent rate performance and long cycle life. At present, porous organic framework materials are considered as promising electrode materials for new generation lithium ion batteries. The porous organic framework material has the advantages of low cost and recoverability, and simultaneously has small heat release amount in the complete discharge process of the battery, so the use safety is high. More importantly, by exploring the efficient lithium storage mechanism of the active functional group in the porous organic framework material structure, the design of the organic electrode material on the molecular level can be guided and realized, so that a large amount of novel electrode materials are developed. However, the porous organic framework electrode material also has some problems in the using process, such as small reversible capacity, poor conductivity, easy dissolution of active substances in organic electrolyte, and the like, and the application and development of the porous organic framework electrode material in the lithium ion storage field are severely restricted by the problems. Aiming at the problems of the application of the porous organic framework material in the lithium battery, researches are carried out to find a suitable carbon material to be compounded with the porous organic framework material so as to enhance the conductivity of the porous organic framework material.
Covalent organic frameworks and metal-organic frameworks are typical representatives of porous organic and inorganic-organic framework materials. The covalent organic framework material is a porous framework with periodic organic structural units, is composed of light elements such as C, N and B through covalent bonds, and is decorated by different functional groups to endow the material with lower weight density and molecular design characteristics. On the other hand, metal-organic framework materials are composed of metal ions or metal-containing clusters (secondary building blocks, SBUs) and coordinating organic ligands via flexible coordination bonds, thereby forming controllable morphology and pore characteristics. For materials with high porosity, covalent organic framework materials or metal organic framework materials, there is generally poor electrical conductivity. This is because the difference between the insulating properties of most organic ligand units and the d orbitals of these conjugated p orbitals or transition metals results in low conductivity or low ionic conductivity, which ultimately will result in low specific charge/discharge capacity.
It has been reported that few purely covalent organic framework materials and metal organic framework materials have high reversible lithium storage capacity so far when used as electrode materials for lithium ion batteries. This is probably due to the limitations of electrochemical energy storage due to the poor conductivity, few active sites, etc. of simple covalent organic framework materials and metal organic framework materials.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to overcome the defects in the prior art and provide a composite organic framework nano electrode material and a preparation method thereof.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
a preparation method of a composite organic framework nano electrode material adopts a one-pot method for microwave stirring synthesis, and obtains the composite organic framework nano material through interconnection and hybridization of a covalent organic framework and a metal organic framework based on Mn-N bonds, and comprises the following steps:
a. weighing 1,3, 5-benzenetricarboxylic acid and 1, 4-diaminobenzene, ultrasonically dispersing in 1-2mL of 1, 4-dioxane, adding 0.1-0.3mL of acetic acid aqueous solution with the molar concentration not lower than 3M into the suspension, further stirring for 4-6h at the room temperature of 20-30 ℃ to obtain yellow solid precipitate, using N, N-dimethylformamide and tetrahydrofuran as solvents, centrifuging the obtained precipitate, using THF as a solvent, performing Soxhlet extraction, drying for 10-12h at the temperature of 60-80 ℃, and collecting to obtain a yellow covalent organic framework material;
preferably, the mass ratio of the 1,3, 5-benzenetricarboxylic aldehyde to the 1, 4-diaminobenzene is 3: 2-2: 3.
b. Weighing a covalent organic framework material and manganese nitrate tetrahydrate, and putting the covalent organic framework material and the manganese nitrate tetrahydrate in 4-6mL of ethanol to prepare a solution A; weighing 1,3, 5-benzene tricarboxylic acid, and dissolving in 4-6mL of ethanol to obtain a solution B; and respectively carrying out ultrasonic dispersion on the solution A and the solution B for 5-10min, mixing, stirring for 20-30min, then placing the mixed solution into a single-mode reactor for reaction, washing precipitates with ethanol after the reaction is finished, drying for 10-12h at 60-80 ℃, and collecting a product obtained by compounding a brown covalent organic framework and a metal organic framework, thereby obtaining the composite organic framework nano electrode material.
Preferably, the mass ratio of the covalent organic framework material to the manganese nitrate tetrahydrate is 1: 5-2: 5;
preferably, the mass ratio of the manganese nitrate tetrahydrate to the 1,3, 5-benzenetricarboxylic acid is 2: 1-3: 1
Preferably, the reaction temperature of the mixed solution in the single-mode reactor is 150-170 ℃, and the reaction time is 20-30 min.
The invention also provides a composite organic framework nano electrode material which is prepared by the preparation method of the composite organic framework nano electrode material.
As a preferred technical scheme of the invention, the composite organic framework nano-electrode material has an adjustable flower-ball-shaped microstructure. The composite organic framework nano electrode material prepared by the invention has lithium storage activity and synergistic effect, manganese in the metal organic framework has redox energy storage activity in the composite electrode, and a conjugated benzene ring in the covalent organic framework has high-capacity lithium storage activity of storing one lithium per carbon after being activated.
Compared with the prior art, the invention has the following obvious and prominent substantive characteristics and remarkable advantages:
1. the composite organic framework nano electrode material not only has an adjustable spherical microstructure, but also can activate a metal center (Mn) in the composite material2+The switching mechanism) and the lithium storage property of C ═ C in the conjugated benzene ring; meanwhile, the preparation process of the composite material has short reaction time, low requirement on equipment and good prospect;
2. the composite organic framework nano material prepared by the invention not only has simple synthesis method and relatively easy realization of synthesis conditions, but also can obtain a hybrid material with uniform appearance, high specific surface area, porous framework and high crystallinity by compounding the covalent organic framework and the metal organic framework; in addition, the construction of the composite organic framework nano material prepared by the invention can overcome the inherent weakness of the single framework, and simultaneously generates synergistic effect, thereby providing multifunctional property for specific application; the application of the composite organic framework nano material prepared by the method in the energy storage direction of the lithium ion battery is a promising industrial direction for further research;
3. the method is simple and easy to implement, low in cost and suitable for popularization and application.
Drawings
Fig. 1 is a photomicrograph of a composite organic framework nano-electrode material prepared in the first embodiment of the invention, wherein a and b in fig. 1 are a Scanning Electron Microscope (SEM) photograph and a Transmission Electron Microscope (TEM) photograph of the composite organic framework nano-electrode material, respectively.
FIG. 2 is a Fourier transform infrared (FI-IR) spectrum of the composite organic frame nano-electrode material prepared in the first embodiment of the invention.
Fig. 3 is a Raman spectrum (Raman) of the composite organic framework nano-electrode material prepared in the first embodiment of the present invention.
Fig. 4 is a small current (0.2C) charge-discharge cycle performance diagram of the composite organic framework nano-electrode material prepared in the first embodiment of the invention.
Detailed Description
The above-described scheme is further illustrated below with reference to specific embodiments, which are detailed below:
the first embodiment is as follows:
in this embodiment, a preparation method of a composite organic framework nano-electrode material, which is synthesized by microwave stirring through a one-pot method, obtains the composite organic framework nano-electrode material through interconnection and hybridization of a covalent organic framework and a metal organic framework based on a Mn-N bond, and includes the following steps:
a. weighing 16mg of 1,3, 5-benzenetricarboxylic acid and 16mg of 1, 4-diaminobenzene, ultrasonically dispersing in 1mL of 1, 4-dioxane, adding 0.2mL of acetic acid aqueous solution with the molar concentration of 3M into the suspension, further stirring for 5 hours at room temperature of 25 ℃ to obtain yellow solid precipitate, using N, N-dimethylformamide and tetrahydrofuran as solvents, centrifuging the obtained precipitate, using THF as a solvent, performing Soxhlet extraction, drying for 12 hours at 60 ℃, and collecting yellow covalent organic framework materials;
b. weighing 13.8mg of covalent organic framework material and 38.4mg of manganese nitrate tetrahydrate in 5mL of ethanol to prepare a solution A; weighing 17.5mg of 1,3, 5-benzene tricarboxylic acid, and dissolving in 5mL of ethanol to prepare a solution B; and respectively carrying out ultrasonic dispersion on the solution A and the solution B for 5min, mixing, stirring for 30min, then placing the mixed solution at 160 ℃, reacting for 30min in a single-mode reactor, washing precipitates with ethanol after the reaction is finished, drying for 12h at 60 ℃, and collecting a product obtained by compounding a brown covalent organic framework and a metal organic framework, thereby obtaining the composite organic framework nano-electrode material.
Experimental test analysis:
the composite organic frame nano-electrode material prepared by the embodiment is used as a sample for property test and performance characterization,
the preparation of the lithium ion battery cathode, the assembly of the battery and the method of the test experiment are as follows:
(1) selecting an organic framework nano composite, acetylene black and a polyvinylidene fluoride adhesive, uniformly mixing the materials in a mass ratio of 8:1:1, adding N, N-dimethyl pyrrolidone into the mixture, dispersing slurry by using a high-speed internal rotation type homogenizer for 5-7 times in one minute each time to obtain uniform black colloidal slurry of the composite organic framework nano material;
(2) uniformly coating the black colloidal slurry on a copper foil current collector with a loading of 2mg cm-2Placing the electrode in a vacuum oven for drying at the temperature of 60 ℃ for 12 hours to obtain the composite organic frame lithium battery electrode material, wherein the thickness of the electrode is not more than 20 mu m;
(3) placing the prepared electrode to be tested into a self-made stainless steel battery die for testing, wherein a lithium sheet is used as a negative electrode, a polypropylene porous membrane (Celgard 2400) is used as a diaphragm, and an electrolyte is 1mol/L LiPF6The cells were assembled with a mixed solution of ethylene carbonate and diethyl carbonate (1: 1w/w) in a glove box filled with high-purity argon gas. In the LAND-CT2001C system, in a fixed potential range (5mV-3.0V vs. Li)+/Li) are lithiated and delithiated at different currents. The test current density was 0.2C, where 1C equals 1000mAg-1The test voltage range is 0.001-3.0V.
As shown in FIG. 1, SEM image and TEM image reveal that the composite organic framework nano-electrode material presents flower-ball-shaped appearance, which is different from the flake-stacking appearance of the original covalent organic framework material and the ball-shaped appearance of the original metal organic framework material, FIG. 2 is a Fourier transform infrared spectrogram of the composite organic framework nano-electrode material, and 1620cm can be observed in infrared spectrum-1The characteristic peaks in (A) correspond to the C ═ N groups formed by dehydration condensation of 1,3, 5-benzenetricarboxylic acid and 1, 4-diaminobenzene in the covalent organic framework, at 1629,1575,1440 and 1374cm-1The characteristic peak of (A) corresponds to COO in the metal-organic framework—The stretching vibration. FIG. 3 is a Raman spectrum of the composite organic framework nanoelectrode material, observed at about 1628cm-1The characteristic peak at (1) corresponds to the C ═ N functional group in the covalent organic framework, and is at-1760 cm-1The characteristic peak at (A) corresponds to the COO in the metal-organic framework—. The Fourier transform infrared spectrogram and the Raman spectrogram of the composite organic framework nano electrode material both show that the composite organic framework nano electrode material is successfully prepared. FIG. 4 shows the small current (0.2C) of the composite organic frame nano-electrode materialThe charge-discharge cycle performance chart shows that as shown in FIG. 4, the composite organic framework nano-electrode material has excellent cycle performance, and the reversible capacity is stabilized at 1020mAh g after 650 cycles of activation-1. The high capacity is mainly in a composite structure, the two components have a synergistic effect, manganese in the metal organic framework has redox energy storage activity in the composite electrode, and a conjugated benzene ring in the covalent organic framework has high capacity lithium storage activity of storing one lithium per carbon after being activated. The preparation process of the composite material has the advantages of short reaction time, low requirement on equipment, excellent battery cycle performance and good prospect.
The composite organic framework nano-electrode material prepared by the embodiment has lithium storage activity and synergistic effect, manganese in the metal organic framework has redox energy storage activity in the composite electrode, and a conjugated benzene ring in the covalent organic framework has high-capacity lithium storage activity of storing one lithium per carbon after being activated. The original metal-organic framework material was also synthesized in a similar process, but without the covalent organic framework material. The composite organic framework nano-electrode material prepared by the embodiment not only has an adjustable flower-ball-shaped microstructure, but also can activate a metal center (Mn) in the composite material2+The switching mechanism) and the lithium storage property of C ═ C in the conjugated benzene rings. Meanwhile, the preparation process of the composite material has short reaction time, low requirement on equipment and good prospect.
Example two:
this example is essentially the same as the first example, and is characterized by the following synthetic process:
in this embodiment, a preparation method of a composite organic framework nano-electrode material, which is synthesized by microwave stirring through a one-pot method, obtains the composite organic framework nano-electrode material through interconnection and hybridization of a covalent organic framework and a metal organic framework based on a Mn-N bond, and includes the following steps:
a. weighing 16mg of 1,3, 5-benzenetricarboxylic acid and 10.7mg of 1, 4-diaminobenzene, ultrasonically dispersing in 2mL of 1, 4-dioxane, adding 0.3mL of aqueous solution of acetic acid with the molar concentration of 3M into the suspension, further stirring at room temperature of 30 ℃ for 6 hours to obtain yellow solid precipitate, using N, N-dimethylformamide and tetrahydrofuran as solvents, centrifuging the obtained precipitate, using THF as a solvent, performing Soxhlet extraction, drying at 80 ℃ for 10 hours, and collecting to obtain a covalent organic framework material;
b. weighing 13.8mg of covalent organic framework material and 34.5mg of manganese nitrate tetrahydrate in 6mL of ethanol to prepare a solution A; weighing 11.5mg of 1,3, 5-benzene tricarboxylic acid, and dissolving in 6mL of ethanol to prepare a solution B; and respectively carrying out ultrasonic dispersion on the solution A and the solution B for 10min, mixing, stirring for 20min, then placing the mixed solution at 150 ℃, reacting for 20min in a single-mode reactor, washing precipitates with ethanol after the reaction is finished, drying for 10h at 80 ℃, and collecting a product obtained by compounding a covalent organic framework and a metal organic framework, thereby obtaining the composite organic framework nano electrode material-B.
The composite organic framework nano electrode material-B prepared by the embodiment is a molecular level hybrid composite organic framework nano electrode material with coordination, the preparation of the composite material is to synthesize a covalent organic framework material based on imine in advance, then the covalent organic framework material is added in the process of synthesizing the metal organic framework material, and the metal center of the metal organic framework material can be coordinated with an amino functional group in the covalent organic framework material to form a Mn-N bond, so that the controlled growth of the covalent organic framework material is realized, and the novel composite organic framework nano electrode material is constructed. The composite organic framework nano-electrode material-B prepared in the embodiment not only has an adjustable flower-ball-shaped microstructure, but also can activate a metal center (Mn) in the composite material2+The switching mechanism) and the lithium storage property of C ═ C in the conjugated benzene rings. Meanwhile, the preparation process of the composite material has short reaction time, low requirement on equipment and good prospect.
Example three:
this example is essentially the same as the first example, and is characterized by the following synthetic process:
in this embodiment, a preparation method of a composite organic framework nano-electrode material, which is synthesized by microwave stirring through a one-pot method, obtains the composite organic framework nano-electrode material through interconnection and hybridization of a covalent organic framework and a metal organic framework based on a Mn-N bond, and includes the following steps:
a. weighing 16mg of 1,3, 5-benzenetricarboxylic acid and 24mg of 1, 4-diaminobenzene, ultrasonically dispersing in 2mL of 1, 4-dioxane, adding 0.3mL of acetic acid aqueous solution with the molar concentration of 3M into the suspension, further stirring for 6 hours at room temperature of 30 ℃ to obtain yellow solid precipitate, using N, N-dimethylformamide and tetrahydrofuran as solvents, centrifuging the obtained precipitate, using THF as a solvent, performing Soxhlet extraction, drying for 10 hours at 80 ℃, and collecting to obtain a covalent organic framework material;
b. weighing 13.8mg of covalent organic framework material and 69mg of manganese nitrate tetrahydrate in 6mL of ethanol to prepare a solution A; weighing 34.5mg of 1,3, 5-benzene tricarboxylic acid, and dissolving in 6mL of ethanol to prepare a solution B; and respectively carrying out ultrasonic dispersion on the solution A and the solution B for 10min, mixing, stirring for 20min, then placing the mixed solution at 170 ℃, reacting for 30min in a single-mode reactor, washing precipitates with ethanol after the reaction is finished, drying for 10h at 80 ℃, and collecting a product obtained by compounding a covalent organic framework and a metal organic framework, thereby obtaining the composite organic framework nano electrode material-C.
The composite organic framework nano-electrode material-C prepared in this example is a novel composite organic framework nano-electrode material constructed by synthesizing an imine-based covalent organic framework material in advance, then adding the covalent organic framework material in the process of synthesizing a metal organic framework material, and coordinating the metal center of the metal organic framework material with an amino functional group in the covalent organic framework material to form a Mn-N bond, thereby realizing the controlled growth of the covalent organic framework material. The composite organic framework nano-electrode material-C prepared by the embodiment has lithium storage activity and synergistic effect, manganese in the metal organic framework has redox energy storage activity in the composite electrode, and a conjugated benzene ring in the covalent organic framework has high-capacity lithium storage activity of storing one lithium per carbon after being activated. Meanwhile, the preparation process of the composite material has short reaction time, low requirement on equipment and good prospect.
The embodiments of the present invention have been described with reference to the accompanying drawings, but the present invention is not limited to the embodiments, and various changes and modifications can be made according to the purpose of the invention, and any changes, modifications, substitutions, combinations or simplifications made according to the spirit and principle of the technical solution of the present invention shall be equivalent substitutions, as long as the purpose of the present invention is met, and the present invention shall fall within the protection scope of the present invention as long as the technical principle and inventive concept of the composite organic frame nano-electrode material and the preparation method thereof are not departed.
Claims (5)
1. A preparation method of a composite organic framework nano electrode material is characterized in that the composite organic framework nano electrode material is synthesized by adopting a one-pot method through microwave stirring, and the composite organic framework nano electrode material is obtained through the interconnection hybridization of a covalent organic framework and a metal organic framework based on Mn-N bonds, and comprises the following steps:
a. weighing 1,3, 5-benzenetricarboxylic acid and 1, 4-diaminobenzene, ultrasonically dispersing in 1-2mL of 1, 4-dioxane, adding 0.1-0.3mL of acetic acid aqueous solution with the molar concentration not lower than 3M into the suspension, further stirring for 4-6h at the room temperature of 20-30 ℃ to obtain yellow solid precipitate, using N, N-dimethylformamide and tetrahydrofuran as solvents, centrifuging the obtained precipitate, using THF as a solvent, performing Soxhlet extraction, drying for 10-12h at the temperature of 60-80 ℃, and collecting to obtain a yellow covalent organic framework material;
b. weighing a covalent organic framework material and manganese nitrate tetrahydrate, and putting the covalent organic framework material and the manganese nitrate tetrahydrate in 4-6mL of ethanol to prepare a solution A; weighing 1,3, 5-benzene tricarboxylic acid, and dissolving in 4-6mL of ethanol to obtain a solution B; and respectively carrying out ultrasonic dispersion on the solution A and the solution B for 5-10min, mixing, stirring for 20-30min, then placing the mixed solution into a single-mode reactor for reaction, washing precipitates with ethanol after the reaction is finished, drying for 10-12h at 60-80 ℃, and collecting a product obtained by compounding a brown covalent organic framework and a metal organic framework, thereby obtaining the composite organic framework nano electrode material.
2. The method for preparing the composite organic framework nano-electrode material according to claim 1, wherein the method comprises the following steps: in the step a, the mass ratio of the 1,3, 5-benzenetricarboxylic aldehyde to the 1, 4-diaminobenzene is 3: 2-2: 3.
3. The method for preparing the composite organic framework nano-electrode material according to claim 1, wherein the method comprises the following steps: in the step b, the mass ratio of the covalent organic framework material to the manganese nitrate tetrahydrate is 2: 5-1: 5;
the mass ratio of the manganese nitrate tetrahydrate to the 1,3, 5-benzenetricarboxylic acid is 3: 1-2: 1;
the reaction temperature of the mixed solution in the single-mode reactor is 150-170 ℃, and the reaction time is 20-30 min.
4. A composite organic framework nano-electrode material is characterized in that: the composite organic framework nano-electrode material is prepared by the preparation method of the composite organic framework nano-electrode material of claim 1.
5. The composite organic framework nanoelectrode material of claim 4, wherein: has an adjustable ball-shaped microstructure.
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Application publication date: 20200918 |