CN111933935A - Copper-based multi-core supramolecular compound electrode and preparation method and application thereof - Google Patents
Copper-based multi-core supramolecular compound electrode and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a supramolecular compound electrode plate for an alkali metal ion battery, which is used for preparing a large-particle copper-based multi-core supramolecular compound and uniformly loading the large-particle copper-based multi-core supramolecular compound on the surface or inside a conductive agent. Firstly, a copper-based multi-core supramolecular compound is prepared by a simple liquid-phase method, and a supramolecular compound-based electrode slice with smooth surface and uniform components is prepared by a simple solid-liquid-solid phase conversion process and is applied to an alkali metal ion battery system. The invention takes common copper salt and organic matter as raw materials, and the supermolecular compound-based electrode with excellent performance is prepared by a simple dissolving-recrystallization method, and has the characteristics of simple and convenient process, large-scale production, excellent comprehensive electrochemical performance of products and the like.
Description
Technical Field
The invention belongs to the field of rechargeable batteries, and relates to a supramolecular compound electrode for an alkali metal ion battery, in particular to a copper-based multi-core supramolecular compound electrode and a preparation method and application thereof.
Background
Among the negative electrode materials of alkali metal ion batteries (lithium ion batteries, sodium ion batteries and potassium ion batteries), supermolecules have the advantages of high specific capacity, wide raw material sources and the like. The copper-based multi-core supramolecular compound is a typical supramolecular compound, has higher theoretical specific capacity when being used for an alkali metal ion battery system, and is a potential alkali metal ion battery electrode material.
Although the copper-based multi-core supramolecular compound-based electrode has the advantages of low raw material cost, high specific capacity and the like, products with high yield and high purity are difficult to prepare by a conventional solid phase method, a coprecipitation method and the like, so that a proper material preparation method needs to be selected. In addition, in the electrode sheet preparation process, if the process parameters such as the conductive agent, the adhesive and the like are not properly selected, the problems of uneven distribution of surface active substances, poor cycle life, poor rate performance and the like of the electrode sheet can be caused, so that a proper electrode sheet preparation process needs to be searched. Patent CN201810000630.7 discloses an iron-copper oxide/copper-based electrode material and a preparation method thereof, the patent is to grow copper hydroxide nanowire array (cu (oh)) on a copper substrate in situ2Copper base, method for electrodeposition in electrolyte containing iron ions by means of constant potentialIn Cu (OH)2Copper-based electrodeposition of iron hydroxide to form hollow tubular structures Fe (OH)3/Cu(OH)2Copper base, then high temperature roasting to convert ferric hydroxide into ferric oxide and copper hydroxide into copper oxide while maintaining the hollow tubular structure, thus obtaining hollow tubular structure Fe3O4CuO/copper-based materials; although the method can prepare the material with high specific volume, the high specific capacitance of the product is realized by a hollow tubular structure; patent CN201610616983.0 discloses a three-dimensional nanoporous copper/one-dimensional cuprous oxide nanowire network type lithium ion battery cathode and a one-step preparation method thereof, the lithium ion battery cathode is composed of a three-dimensional nanoporous copper substrate and a cuprous oxide nanowire layer, the substrate is used as a current collector, the cuprous oxide nanowire layer is used as an active lithium storage layer, the cuprous oxide nanowire layer is positioned on the surface of the substrate and combined with the substrate into a whole, the cuprous oxide nanowire layer is formed by interweaving and stacking cuprous oxide nanowires growing in situ on the substrate, and the cuprous oxide nanowire layer is in a network structure. According to the patent, the three-dimensional nano porous copper substrate is used as a current collector without adding an adhesive, so that the internal resistance of the lithium ion battery is reduced, and the conductivity of the lithium ion battery is improved; but the finally obtained first discharge specific capacity under the current density of 0.1mA/cm is 2.3-3.0mAh/cm, and the requirement of the modern society on the high specific volume battery can not be met.
Disclosure of Invention
In order to solve the technical problems, the invention provides a copper-based multi-core supramolecular compound electrode and a preparation method and application thereof aiming at the problems or improvement requirements in the practical application of the copper-based multi-core supramolecular compound electrode.
The technical scheme of the invention is realized as follows:
a preparation method of a copper-based multi-core supramolecular compound electrode comprises the following steps: the copper salt and the organic ligand are used as raw materials, the large-particle copper-based multi-core supramolecular compound is prepared by a liquid phase method, and the large-particle copper-based multi-core supramolecular compound is converted into nano particles through a simple dissolving-recrystallization process and is uniformly loaded in and on the surface of conductive carbon, so that the copper-based multi-core supramolecular compound electrode is obtained.
The preparation method of the copper-based multi-core supramolecular compound electrode comprises the following steps:
(1) dissolving a copper salt in a solvent I, stirring until the copper salt is dissolved, adding an organic ligand, then placing the mixture in a reaction kettle for reaction, and washing and drying the mixture after the reaction is finished to obtain a large-particle copper-based multi-core supramolecular compound;
(2) and (2) dissolving the large-particle copper-based multi-core supramolecular compound prepared in the step (1) in a solvent II, stirring until the large-particle copper-based multi-core supramolecular compound is dissolved, adding a conductive agent and an adhesive, uniformly stirring, coating the mixture on a copper foil, and performing vacuum drying to obtain the copper-based multi-core supramolecular compound electrode.
The copper salt in the step (1) is one or more of copper sulfate, copper nitrate, copper chloride or acetic acid ketone; the solvent I is one or more of methanol, ethanol, acetone or ethylene glycol.
The organic ligand is pyridine-3-formaldehyde and dichloromethane in a volume ratio of 4:1, and each mL of the organic ligand reacts with 0.1-1.5 g of copper salt.
The reaction condition in the step (1) is that the reaction temperature is 70-100 ℃, and the reaction time is 36-120 h.
In the step (2), the solvent II is one or more of N-methyl pyrrolidone, water, methanol, ethanol or glycerol; the conductive agent is one or more of acetylene black, Ketjen black or biomass carbon; the adhesive is one or more of polyvinylidene fluoride, polytetrafluoroethylene, sodium polyacrylate or sodium carboxymethylcellulose.
The mass ratio of the large-particle copper-based multi-core supramolecular compound to the conductive agent to the adhesive is 7: 2: 1, 0.1 to 1.0 g of the compound is dissolved in each mL of the solvent II.
The vacuum drying condition in the step (2) is drying for 6-24h at 60-100 ℃.
The copper-based multi-core supramolecular compound electrode prepared in a large scale by the method is provided.
The specific capacity of the alkali metal ion battery containing the copper-based multi-core supramolecular compound electrode can reach 1021.8 mA h/g after 50 cycles of circulation
The invention has the following beneficial effects:
1. the application utilizes a simple liquid phase method to prepare the copper-based multi-core supramolecular compound, and prepares the supramolecular compound-based electrode slice with smooth surface and uniform components through a simple solid-liquid-solid phase conversion process, and the supramolecular compound-based electrode slice is applied to an alkali metal ion battery system. Preparing micron-sized copper-based multi-core supramolecular compound monocrystal particles by a solution method; selecting a specific solvent to dissolve the copper-based multi-core supramolecular compound by a dissolution method, and mixing the copper-based multi-core supramolecular compound with a conductive agent and a binding agent to prepare electrode plate slurry; the uniform loading of the copper-based multi-core supramolecular compound nanoparticles on the surface or inside the carbon material is realized through a simple drying process.
2. According to the invention, large-particle copper-based multi-core supramolecular compound single crystals are converted into superfine nano particles and are uniformly loaded on the surface or inside of the conductive carbon material, so that the copper-based multi-core supramolecular compound-based electrode slice is obtained. Aiming at the optimization of the electrode slice, the electron/ion migration path in the charging and discharging process is shortened, and the dispersibility and the utilization rate of the active material in the conductive agent are improved. When the electrode plate is used as a lithium ion battery material, the reversible specific capacity of the first loop of the electrode plate reaches 843.6 mA h/g under the current density of 200 mA/g.
3. After the copper-based multi-core supramolecular compound nanoparticles are uniformly loaded on the surface or inside the carbon material, the electrode has low overall impedance and high rate performance due to the good contact between the active material and the conductive agent. When the electrode plate is used as a lithium ion battery material, the specific capacity of the electrode plate can reach 459.4 mA h/g at the maximum under the current density of 2000 mA/g, and the electrode plate shows good rapid charge and discharge performance.
4. According to the invention, a dissolution-recrystallization method is used for converting the large-particle copper-based multi-core supramolecular compound into nano-particles with uniform particle size, so that particle pulverization and irreversible capacity loss in the charging and discharging processes are reduced, and the stability of an electrode structure is improved. The prepared electrode has specific capacity of 1021.8 mA h/g after circulating for 50 circles in the lithium ion battery, and shows good structural stability and cycle performance.
5. The method has the advantages that the raw material source is wide, the raw material source is simple and convenient, the raw material is easy to obtain, and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a photograph under a microscope of a supramolecular compound in example 1 of the present invention.
Figure 2 is an X-ray diffraction diagram of the supramolecular compound in example 2 of the invention.
FIG. 3 is the elemental composition of the supramolecular compound in example 4 of the invention.
Fig. 4-6 are scanning electron micrographs of the supramolecular compound electrode slices prepared in examples 1, 3 and 4, respectively, of the invention.
Fig. 7 is a cycle performance diagram of the supramolecular compound electrode sheet prepared in example 3 of the invention in a lithium ion battery.
Fig. 8 is a graph of rate performance of the supramolecular compound electrode sheet prepared in example 3 of the invention in a lithium ion battery.
Fig. 9 is a graph of rate performance of the supramolecular compound electrode sheet prepared in example 4 of the invention in a sodium ion battery.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
A preparation method of a copper-based multi-core supramolecular compound electrode comprises the following steps:
(1) weighing 0.24 g of copper acetate, dissolving in 20 mL of methanol, and stirring until the copper acetate is dissolved; 0.12 mL of pyridine-3-formaldehyde is weighed and dissolved in the solution, and then 0.3 mL of dichloromethane is added; putting the solution into a reaction kettle with the capacity of 30 mL, heating to 100 ℃, and preserving heat for 48 hours; washing the reaction product with ethanol/water (volume ratio 1: 1) mixture, and drying in a vacuum oven to obtain the reaction product, wherein the micrograph is shown in figure 1, and the obtained product is tetradecahedron particles with smooth surfaces and clear edges and corners;
(2) weighing 0.7 g of the reaction product, adding the reaction product into 2 mL of N-methyl-pyrrolidone, and stirring for 1 h until the particles are completely dissolved; then adding 0.2 g of acetylene black and 0.1 g of polyvinylidene fluoride, stirring uniformly and then uniformly coating on the copper foil; and (3) placing the copper foil in a vacuum drying oven, and drying at 80 ℃ for 12 hours to obtain the final electrode slice.
Example 2
A preparation method of a copper-based multi-core supramolecular compound electrode comprises the following steps:
(1) weighing 0.29 g of copper nitrate, dissolving in 20 mL of methanol, and stirring until the copper nitrate is dissolved; 0.12 mL of pyridine-3-formaldehyde is weighed and dissolved in the solution, and then 0.3 mL of dichloromethane is added; putting the solution into a reaction kettle with the capacity of 30 mL, heating to 80 ℃, and preserving heat for 60 hours; washing the reaction product with a mixture of ethanol and water (volume ratio 1: 1), and drying in a vacuum oven to obtain the reaction product, wherein the X-ray diffraction pattern of the reaction product is shown in figure 2, and the compound has good crystallinity;
(2) weighing 0.7 g of the reaction product, adding the reaction product into 2 mL of N-methyl-pyrrolidone, and stirring for 1 h until the particles are completely dissolved; then adding 0.2 g of acetylene black and 0.1 g of polyvinylidene fluoride, stirring uniformly and then uniformly coating on the copper foil; and (3) placing the copper foil in a vacuum drying oven, and drying at 80 ℃ for 12 hours to obtain the final electrode slice.
Example 3
A preparation method of a copper-based multi-core supramolecular compound electrode comprises the following steps:
(1) weighing 0.21 g of copper chloride, dissolving in 20 mL of methanol, and stirring until the copper chloride is dissolved; 0.12 mL of pyridine-3-formaldehyde is weighed and dissolved in the solution, and then 0.3 mL of dichloromethane is added; putting the solution into a reaction kettle with the capacity of 30 mL, heating to 100 ℃, and preserving heat for 80 hours; washing the reaction product by using an ethanol/water (volume ratio is 1: 1) mixture, and drying in a vacuum oven to obtain a reaction product;
(2) weighing 0.7 g of the reaction product, adding the reaction product into 2 mL of N-methyl-pyrrolidone, and stirring for 1 h until the particles are completely dissolved; then adding 0.2 g of acetylene black and 0.1 g of polyvinylidene fluoride, stirring uniformly and then uniformly coating on the copper foil; and (3) placing the copper foil in a vacuum drying oven, and drying at 80 ℃ for 12 hours to obtain the final electrode slice.
Example 4
A preparation method of a copper-based multi-core supramolecular compound electrode comprises the following steps:
(1) weighing 0.21 g of copper chloride, dissolving in 20 mL of methanol, and stirring until the copper chloride is dissolved; 0.12 mL of pyridine-3-formaldehyde is weighed and dissolved in the solution, and then 0.3 mL of dichloromethane is added; putting the solution into a reaction kettle with the capacity of 30 mL, heating to 70 ℃, and preserving heat for 120 hours; washing the reaction product with ethanol/water (volume ratio 1: 1) mixture, and drying in a vacuum oven to obtain the detection result of the reaction product shown in figure 4, wherein the compound mainly comprises Cu, C, N, O, Cl and other elements;
(2) weighing 0.7 g of the reaction product, adding the reaction product into 2 mL of N-methyl-pyrrolidone, and stirring for 1 h until the particles are completely dissolved; then adding 0.2 g of acetylene black and 0.1 g of polyvinylidene fluoride, stirring uniformly and then uniformly coating on the copper foil; and (3) placing the copper foil in a vacuum drying oven, and drying at 80 ℃ for 12 hours to obtain the final electrode slice.
Fig. 4, 5, and 6 are scanning electron microscope images of supramolecular compound electrode sheets prepared in examples 1, 3, and 4, respectively, of the present invention, and although different process conditions are adopted in examples 1, 3, and 4, the surfaces of the electrode sheets prepared by the present invention are covered with a layer of nanoparticles having a uniform particle size, which indicates that the surface components of the electrode sheets are uniform and have no obvious cracks.
Example 5
A preparation method of a copper-based multi-core supramolecular compound electrode comprises the following steps:
(1) weighing 0.29 g of copper nitrate, dissolving in 20 mL of methanol, and stirring until the copper nitrate is dissolved; 0.12 mL of pyridine-3-formaldehyde is weighed and dissolved in the solution, and then 0.3 mL of dichloromethane is added; putting the solution into a reaction kettle with the capacity of 30 mL, heating to 100 ℃, and preserving heat for 36 hours; washing the reaction product by using an ethanol/water (volume ratio is 1: 1) mixture, and drying in a vacuum oven to obtain a reaction product;
(2) weighing 0.7 g of the reaction product, adding the reaction product into 2 mL of N-methyl-pyrrolidone, and stirring for 1 h until the particles are completely dissolved; then adding 0.2 g of acetylene black and 0.1 g of polyvinylidene fluoride, stirring uniformly and then uniformly coating on the copper foil; and (3) placing the copper foil in a vacuum drying oven, and drying for 24 hours at 80 ℃ to obtain the final electrode plate.
Example 6
A preparation method of a copper-based multi-core supramolecular compound electrode comprises the following steps:
(1) weighing 0.21 g of copper chloride, dissolving in 20 mL of ethylene glycol, and stirring until the copper chloride is dissolved; 0.12 mL of pyridine-3-formaldehyde is weighed and dissolved in the solution, and then 0.3 mL of dichloromethane is added; putting the solution into a reaction kettle with the capacity of 30 mL, heating to 80 ℃, and preserving heat for 120 hours; washing the reaction product by using an ethanol/water (volume ratio is 1: 1) mixture, and drying in a vacuum oven to obtain a reaction product;
(2) weighing 0.7 g of the reaction product, adding the reaction product into 2 mL of N-methyl-pyrrolidone, and stirring for 1 h until the particles are completely dissolved; then adding 0.2 g of acetylene black and 0.1 g of polyvinylidene fluoride, stirring uniformly and then uniformly coating on the copper foil; and (3) placing the copper foil in a vacuum drying oven, and drying for 24 hours at 60 ℃ to obtain the final electrode slice.
Example 7
A preparation method of a copper-based multi-core supramolecular compound electrode comprises the following steps:
(1) weighing 0.63 g of copper chloride, dissolving in 20 mL of ethanol, and stirring until the copper chloride is dissolved; 0.12 mL of pyridine-3-formaldehyde is weighed and dissolved in the solution, and then 0.3 mL of dichloromethane is added; putting the solution into a reaction kettle with the capacity of 30 mL, heating to 80 ℃, and preserving heat for 120 hours; washing the reaction product by using an ethanol/water (volume ratio is 1: 1) mixture, and drying in a vacuum oven to obtain a reaction product;
(2) weighing 0.7 g of the reaction product, adding the reaction product into 7 mL of nitrogen-dimethylformamide, and stirring for 1 h until the particles are completely dissolved; then adding 0.2 g of acetylene black and 0.1 g of polyvinylidene fluoride, stirring uniformly and then uniformly coating on the copper foil; and (3) placing the copper foil in a vacuum drying oven, and drying for 6 hours at 100 ℃ to obtain the final electrode slice.
Example 8
A preparation method of a copper-based multi-core supramolecular compound electrode comprises the following steps:
(1) weighing 0.21 g of copper chloride, dissolving in 20 mL of ethanol, and stirring until the copper chloride is dissolved; 0.6 mL of pyridine-3-formaldehyde is weighed and dissolved in the solution, and then 1.5 mL of dichloromethane is added; putting the solution into a reaction kettle with the capacity of 30 mL, heating to 80 ℃, and preserving heat for 120 hours; washing the reaction product by using an ethanol/water (volume ratio is 1: 1) mixture, and drying in a vacuum oven to obtain a reaction product;
(2) weighing 0.7 g of the reaction product, adding the reaction product into 0.7 mL of glycerol, and stirring for 1 h until the particles are completely dissolved; then adding 0.2 g of Ketjen black and 0.1 g of polytetrafluoroethylene, uniformly stirring and then uniformly coating the mixture on a copper foil; and (3) placing the copper foil in a vacuum drying oven, and drying at 80 ℃ for 12 hours to obtain the final electrode slice.
Examples of the effects of the invention
After the electrode plates prepared in examples 3 and 4 were prepared into batteries, electrochemical performance tests were performed, and the following steps were performed:
1. assembly of lithium ion batteries
The electrode sheet of the above example was each cut into a wafer having a diameter of 8 mm, and the amount of the active material loaded (active material areal density of about 2 to 3 mg/cm) was measured and calculated2). The assembly of the CR-2032 button cell is completed in an argon-protected glove box, the wafer electrode is used as a working electrode, a commercial lithium sheet is used as a counter electrode, a Celgrad 2400 composite membrane is used as a diaphragm, and 1 mol/L LiPF is used6The solution is electrolyte (the solvent is mixed solution of ethylene carbonate/diethyl carbonate/dimethyl carbonate in a volume ratio of 1:1: 1), and the solution is packaged by a packaging machine after being assembled. And after the battery is assembled, standing for 10 hours and then carrying out electrochemical performance test.
2. Sodium ion battery assembly
The electrode sheet of the above example was die-cut into a circular piece having a diameter of 8 mm, and the active material loading (active material areal density of about 2 to 3 mg/cm) thereof was weighed and calculated2). The assembly of the CR-2032 button cell is completed in an argon-protected glove box, the wafer electrode is taken as a working electrode, a self-made sodium sheet is taken as a counter electrode (the diameter is about 12 mm, the thickness is about 2 mm), a glass fiber filter membrane is taken as a diaphragm, and 1 mol/L NaClO is taken4The solution is electrolyte (the solvent is a mixed solution of ethylene carbonate and propylene carbonate with the volume ratio of 1: 1), and the solution is packaged by a packaging machine after the assembly is finished. And after the battery is assembled, standing for 10 hours and then carrying out electrochemical performance test.
3. Electrochemical performance test
Fig. 7 shows the cycle performance of the supramolecular compound electrode sheet prepared in example 3 of the invention in a lithium ion battery. As can be seen from the figure, the specific capacity of the first circle of the electrode can reach 843.6 mA h/g, the specific capacity after 50 circles of circulation is 1021.8 mA h/g, the coulombic efficiency is close to 100%, and the good cycle life of the electrode is proved.
Fig. 8 shows the rate capability of the supramolecular compound electrode sheet prepared in example 3 of the invention in a lithium ion battery. As can be seen from the figure, the specific capacity of the electrode under the large current density of 2000 mA/g can reach 459.4 mA h/g at most, and the specific capacity is still stable when the current density is frequently changed. The multiplying power test result shows that the electrode shows excellent high-current charge-discharge performance and good structural stability in the lithium ion battery.
Fig. 9 shows the rate capability of the supramolecular compound electrode plate prepared in example 4 of the invention in a sodium ion battery. As can be seen from the figure, the specific capacity of the electrode can reach 786.8 mA h/g under the current density of 100 mA/g, and the specific capacity can reach 190.4 mA h/g under the current density of 1000 mA/g, which proves the good cycle life of the electrode. The multiplying power test result shows that the electrode shows good high-current charge and discharge performance in the sodium ion battery.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of a copper-based multi-core supramolecular compound electrode is characterized by comprising the following steps: the copper salt and the organic ligand are used as raw materials, the large-particle copper-based multi-core supramolecular compound is prepared by a liquid phase method, and the large-particle copper-based multi-core supramolecular compound is converted into nano particles through a simple dissolving-recrystallization process and is uniformly loaded in and on the surface of conductive carbon, so that the copper-based multi-core supramolecular compound electrode is obtained.
2. The method for preparing the copper-based multi-core supramolecular compound electrode according to claim 1, characterized in that the steps are as follows:
(1) dissolving a copper salt in a solvent I, stirring until the copper salt is dissolved, adding an organic ligand, then placing the mixture in a reaction kettle for reaction, and washing and drying the mixture after the reaction is finished to obtain a large-particle copper-based multi-core supramolecular compound;
(2) and (2) dissolving the large-particle copper-based multi-core supramolecular compound prepared in the step (1) in a solvent II, stirring until the large-particle copper-based multi-core supramolecular compound is dissolved, adding a conductive agent and an adhesive, uniformly stirring, coating the mixture on a copper foil, and performing vacuum drying to obtain the copper-based multi-core supramolecular compound electrode.
3. The method for preparing copper-based multi-core supramolecular compound electrodes according to claim 2, characterized in that: the copper salt in the step (1) is one or more of copper sulfate, copper nitrate, copper chloride or acetic acid ketone; the solvent I is one or more of methanol, ethanol, acetone or ethylene glycol.
4. The method for preparing copper-based multi-core supramolecular compound electrodes according to claim 3, characterized in that: the organic ligand is pyridine-3-formaldehyde and dichloromethane in a volume ratio of 4:1, and each mL of the organic ligand reacts with 0.1-1.5 g of copper salt.
5. The method for preparing copper-based multi-core supramolecular compound electrodes according to claim 2, characterized in that: the reaction condition in the step (1) is that the reaction temperature is 70-100 ℃, and the reaction time is 36-120 h.
6. The method for preparing copper-based multi-core supramolecular compound electrodes according to claim 2, characterized in that: in the step (2), the solvent II is one or more of N-methyl pyrrolidone, water, methanol, ethanol or glycerol; the conductive agent is one or more of acetylene black, Ketjen black or biomass carbon; the adhesive is one or more of polyvinylidene fluoride, polytetrafluoroethylene, sodium polyacrylate or sodium carboxymethylcellulose.
7. The method for preparing copper-based multi-core supramolecular compound electrodes according to claim 6, characterized in that: the mass ratio of the large-particle copper-based multi-core supramolecular compound to the conductive agent to the adhesive is 7: 2: 1, 0.1 to 1.0 g of the compound is dissolved in each mL of the solvent II.
8. The method for preparing copper-based multi-core supramolecular compound electrodes according to claim 2, characterized in that: the vacuum drying condition in the step (2) is drying for 6-24h at 60-100 ℃.
9. Copper-based multi-core supramolecular compound electrodes prepared on a large scale by the method of any one of claims 1 to 8.
10. Alkali metal ion battery comprising the copper-based multi-core supramolecular compound electrode according to claim 9, characterized in that: the specific capacity of the alkali metal ion battery reaches 1021.8 mA h/g after 50 cycles.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114371205A (en) * | 2022-01-17 | 2022-04-19 | 中原工学院 | Hydrogen peroxide sensor electrode, preparation method and hydrogen peroxide sensor |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103041778A (en) * | 2012-12-28 | 2013-04-17 | 浙江大学 | Metal-organic frame material for absorbing and storing acetylene and preparation method thereof |
| CN107163039A (en) * | 2017-05-11 | 2017-09-15 | 浙江工业大学 | A kind of preparation method of the formaldehyde of 6 methyl 2 p-methylphenyl imidazo [1,2 a] pyridine 3 |
| CN108666573A (en) * | 2018-04-23 | 2018-10-16 | 曲靖师范学院 | A kind of preparation method of titanium-based MOF lithium ion battery negative materials |
| CN109037615A (en) * | 2018-07-08 | 2018-12-18 | 启东祥瑞建设有限公司 | A kind of preparation method of Cu-MOF/rGO lithium ion battery negative material |
| CN109873157A (en) * | 2019-01-26 | 2019-06-11 | 南京理工大学 | Co for lithium ion battery2(BDC)2Ted negative electrode material |
| US10647733B2 (en) * | 2014-03-28 | 2020-05-12 | The University Of Chicago | Metal-organic frameworks containing nitrogen-donor ligands for efficient catalytic organic transformations |
-
2020
- 2020-08-12 CN CN202010805817.1A patent/CN111933935B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103041778A (en) * | 2012-12-28 | 2013-04-17 | 浙江大学 | Metal-organic frame material for absorbing and storing acetylene and preparation method thereof |
| US10647733B2 (en) * | 2014-03-28 | 2020-05-12 | The University Of Chicago | Metal-organic frameworks containing nitrogen-donor ligands for efficient catalytic organic transformations |
| CN107163039A (en) * | 2017-05-11 | 2017-09-15 | 浙江工业大学 | A kind of preparation method of the formaldehyde of 6 methyl 2 p-methylphenyl imidazo [1,2 a] pyridine 3 |
| CN108666573A (en) * | 2018-04-23 | 2018-10-16 | 曲靖师范学院 | A kind of preparation method of titanium-based MOF lithium ion battery negative materials |
| CN109037615A (en) * | 2018-07-08 | 2018-12-18 | 启东祥瑞建设有限公司 | A kind of preparation method of Cu-MOF/rGO lithium ion battery negative material |
| CN109873157A (en) * | 2019-01-26 | 2019-06-11 | 南京理工大学 | Co for lithium ion battery2(BDC)2Ted negative electrode material |
Non-Patent Citations (1)
| Title |
|---|
| 何雄 庞海霞: "一种新型四核铜(Ⅱ)簇配合物的合成及性质表征", 《华中师范大学学报(自然科学版)》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114371205A (en) * | 2022-01-17 | 2022-04-19 | 中原工学院 | Hydrogen peroxide sensor electrode, preparation method and hydrogen peroxide sensor |
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