CN114005683B - CoZn-MOF/NiCo 2 O 4 Preparation method of @ CNTs/rGO composite electrode material - Google Patents

CoZn-MOF/NiCo 2 O 4 Preparation method of @ CNTs/rGO composite electrode material Download PDF

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CN114005683B
CN114005683B CN202111168805.3A CN202111168805A CN114005683B CN 114005683 B CN114005683 B CN 114005683B CN 202111168805 A CN202111168805 A CN 202111168805A CN 114005683 B CN114005683 B CN 114005683B
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钱军
严学庆
袁朝勇
赵荣兴
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JIANGSU OLITER ENERGY TECHNOLOGY CO LTD
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
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    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/46—Metal oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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    • Y02E60/13—Energy storage using capacitors

Abstract

The invention discloses a CoZn-MOF/NiCo 2 O 4 A preparation method of @ CNTs/rGO composite electrode material belongs to the technical field of composite electrode materials, and the invention uses Co (NO) 3 ) 2 ·6H 2 O、Ni(NO 3 ) 2 ·6H 2 O、Zn(NO 3 ) 2 ·6H 2 O, urea, NH 4 F. 2-methylimidazole, GO and carbon nano tube are taken as raw materials, and NiCo is obtained by a hot solvent method 2 O 4 The composite CoZn-MOF/NiCo2O4@ CNTs/rGO electrode material is synthesized by a chemical soaking reaction method and annealing treatment. The electrode material takes graphene and carbon nanotubes as substrates, so that the flexibility and the conductivity of the material are enhanced, the use of an adhesive is avoided, the integral conductivity of the material is greatly improved, the specific surface area of a film is maximized, and the electrode material is favorable for the conduction of electrons and the transmission of ions in a solution.

Description

CoZn-MOF/NiCo 2 O 4 Preparation method of @ CNTs/rGO composite electrode material
Technical Field
The invention belongs to the technical field of composite electrode materials, and particularly relates to CoZn-MOF/NiCo derived from MOF 2 O 4 Generation of nano particlesA preparation method of a composite electrode growing on graphene and carbon nano tubes, namely a CoZn-MOF/NiCo 2 O 4 A preparation method of a @ CNTs/rGO composite electrode material.
Background
Since the 21 st century, the problems of environmental pollution and energy shortage due to excessive use of fossil fuels have become serious, and it is one of the major challenges to develop a pollution-free new energy source and to design a new environment-friendly energy storage device. The super capacitor is a novel energy storage device between the electrostatic capacitor and the traditional chemical power supply, and is widely applied to the fields of electronic equipment, hybrid electric vehicles, standby power supply systems and the like due to the advantages of high power density, excellent rate performance, fast charge and discharge speed, extremely long cycle life and the like. The electrode material is the core part of the super capacitor, and the development of the novel electrode material is a crucial step for researching the novel energy storage device.
Recently, metal Organic Frameworks (MOFs), as a new material with superior characteristics of high surface area, adjustable pore size distribution, structure customizability, etc., are considered as an effective precursor for preparing porous nanostructured electrodes. Among them, the ternary metal oxides and porous carbon materials derived from MOFs have been widely used in many fields including gas separation and adsorption, catalysis, sensing, and drug delivery.
CoZn-MOF derived ternary metal oxides, in particular CoZn-MOF/NiCo, are known 2 O 4 The electrode material is one of the most popular electrode materials for high-performance Super Capacitors (SC) and Lithium Ion Batteries (LIB) due to the advantages of high specific surface area, adjustable pore structure and the like, and can effectively enhance electron/ion transmission kinetics and further obtain higher electrochemical performance. However, if the CoZn-MOF derivative nanopowder is used alone as an electrode material, it is difficult to obtain desirable electrochemical properties due to its disadvantages such as extremely poor conductivity and cycling stability. In recent years, the construction of CoZn-MOF derived ternary metal oxide CoZn-MOF/NiCo 2 O 4 And graphene and carbon nanotubes (CNTs/rGO) is a composite electrode material for improving conductivity, actual specific capacity and stable circulationEffective method for treating hypertension. On the other hand, graphene (GO) is a single-layer carbon-based material with ultrahigh conductivity, can form a unique two-dimensional honeycomb lattice structure, and can effectively improve the conductivity of the composite material so as to improve the specific capacity of the material. To date, there is no CoZn-MOF/NiCo derivative of CoZn-MOF 2 O 4 Reports that nano particles grow on graphene and carbon nano tubes to prepare composite electrode materials and apply the composite electrode materials to the aspect of super capacitors.
Disclosure of Invention
In view of the above problems in the prior art, the first technical problem to be solved by the present invention is to provide a CoZn-MOF/NiCo 2 O 4 A preparation method of a @ CNTs/rGO composite electrode material; the second technical problem to be solved by the invention is to provide the CoZn-MOF/NiCo prepared by the method 2 O 4 The @ CNTs/rGO composite electrode material has a microscopic state lower surface loaded with a structure of attaching flower balls in a flaky nano array; the third technical problem to be solved by the invention is to provide the CoZn-MOF/NiCo 2 O 4 The application of the @ CNTs/rGO composite electrode material in serving as a supercapacitor material.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
CoZn-MOF/NiCo 2 O 4 A preparation method of the @ CNTs/rGO composite electrode material comprises the following steps:
1) Uniformly mixing and stirring the carbon nano tube and GO dispersion liquid, and performing vacuum filtration to obtain a CNTs/GO membrane; adding Co (NO) 3 ) 2 ·6H 2 O、Ni(NO 3 ) 2 ·6H 2 O, urea and NH 4 Adding F into deionized water, mixing and stirring at room temperature to obtain mixed solution, co (NO) 3 ) 2 ·6H 2 O、Ni(NO 3 ) 2 ·6H 2 O, urea and NH 4 The mass ratio of F is 0.5-0.7:0.2-0.5:0.2-0.4:0.05-0.08; urea and NH 4 The molar concentration ratio of F is 0.20-0.30:0.05-0.08; transferring the mixed solution into a reaction kettle, immersing the CNTs/GO membrane into the mixed solution, keeping the temperature at 110 ℃ for 4 hours, naturally cooling to room temperature, taking out the product, and adding deionized waterWashing with ethanol alternately, and drying to obtain NiCo 2 O 4 @ CNTs/rGO composite films;
2) Preparation of Co (NO) 3 ) 2 ·6H 2 O、Zn(NO 3 ) 2 ·6H 2 Fully dissolving O and 2-methylimidazole solution by ultrasonic, and uniformly mixing and stirring to obtain a CoZn-MOF suspension; mixing said NiCo 2 O 4 The @ CNTs/rGO composite film is immersed in the CoZn-MOF suspension for 0.5 h-6 h to obtain the CoZn-MOF/NiCo 2 O 4 @ CNTs/rGO composite electrode materials; the Co (NO) 3 ) 2 ·6H 2 O and Zn (NO) 3 ) 2 ·6H 2 The mass ratio of O is 0.5-0.7:0.3-0.5; the molar concentration of the 2-methylimidazole solution is 0.39-0.45mol/L;
3) For the CoZn-MOF/NiCo prepared in the step 2) 2 O 4 And carrying out annealing treatment on the @ CNTs/rGO composite electrode material, wherein the annealing temperature is 350 ℃, and the annealing time is 2h.
The graphene and carbon nanotube film surface loaded NiCo are prepared by a simple and rapid thermal solvent method 2 O 4 Materials, i.e. NiCo 2 O 4 @ CNTs/rGO composite films; then the CoZn-MOF/NiCo is synthesized by a simple chemical soaking reaction method and annealing treatment 2 O 4 @ CNTs/rGO composite electrode materials.
Further, in the step 1), the concentration of the GO dispersion liquid is 0.2mg/mL; the carbon nano tube and GO dispersion liquid are mixed and stirred uniformly according to the volume ratio of 1: 500.
Further, in step 1), ni (NO) 3 ) 2 ·6H 2 O、Co(NO 3 ) 2 ·6H 2 O, urea and NH 4 The volume ratio of the F solution is 1: 1-1.2: 1.
Preferably, in step 1), ni (NO) 3 ) 2 ·6H 2 O、Co(NO 3 ) 2 ·6H 2 O, urea and NH 4 The volume ratio of the F solution is 1:1.
Further, in step 2), co (NO) 3 ) 2 ·6H 2 O and Zn (NO) 3 ) 2 ·6H 2 O solutionFirstly, uniformly mixing and stirring the components in a volume ratio of 1:1 to obtain a mixed nitrate solution; and mixing and stirring the mixed nitrate solution and the 2-methylimidazole solution again uniformly at the volume ratio of 2:1 to obtain a CoZn-MOF suspension.
Further, in the step 2), niCo is added 2 O 4 The @ CNTs/rGO composite film is immersed in the CoZn-MOF suspension for 1h.
Further, in the step 3), the annealing temperature is increased to 350 ℃ at a heating rate of 2-5 ℃/min.
The CoZn-MOF/NiCo prepared by the method 2 O 4 @ CNTs/rGO composite electrode materials. The size is about 1cmx2cm, the cutting can be carried out at will according to the actual situation, and the surface of the microscopic state is loaded with the attaching flower ball structure in the flaky nanometer array.
The CoZn-MOF/NiCo 2 O 4 The application of the @ CNTs/rGO composite electrode material as a supercapacitor material.
CoZn-MOF/NiCo 2 O 4 The @ CNTs/rGO composite electrode material is used as a positive electrode material, 6mol/L KOH is used as electrolyte, activated carbon, conductive carbon black and polytetrafluoroethylene are uniformly mixed and dispersed in absolute ethyl alcohol according to the mass ratio of 8:1, then the mixture is coated on foamed nickel, and the foamed nickel is dried and pressed into sheets to prepare electrode sheets serving as the negative electrode material of the supercapacitor.
Performing electrochemical performance tests such as Cyclic Voltammetry (CV) and constant current charging and discharging in a two-electrode system, and calculating corresponding energy density and power density to evaluate the prepared CoZn-MOF/NiCo 2 O 4 Electrochemical properties of @ CNTs/rGO composite films. Wherein the voltage range of the Cyclic Voltammetry (CV) test is 0-1.7V, the scanning speed is 2, 5, 10, 20, 50 and 100mV/s, the voltage range of the constant current charge-discharge test is 0-1.7V, and the current density is 1, 2, 3, 5, 8 and 10A/g.
Because the graphene can be widely applied to portable electronic devices by virtue of good flexibility, compared with other flexible materials, the graphene has good conductivity, and the flaky nano array loaded on the surface of the graphene and the hollow polyhedral structure taking the MOF as the framework are more favorable for storage and movement of charges.
Compared with the prior art, the invention has the beneficial effects that:
the invention synthesizes the CoZn-MOF/NiCo through three steps of a very simple hot solvent method, a chemical soaking reaction method and annealing treatment 2 O 4 @ CNTs/rGO composite electrode materials. The flexibility and the conductivity of the material are greatly enhanced by taking the graphene and the carbon nano tubes as substrates, and meanwhile, coZn-MOF/NiCo derived from the CoZn-MOF 2 O 4 The nano particles directly grow on the graphene and the carbon nano tubes in situ, so that the use of an adhesive is avoided, the impedance of the material is reduced, the integral conductivity of the material is greatly improved, the specific surface area of the film is maximized, and the conductive film is favorable for electron conduction and ion transmission in a solution.
Drawings
FIG. 1 is a CoZn-MOF/NiCo sample prepared in example 2 2 O 4 XRD diffraction pattern of @ CNTs/rGO composite electrode material;
FIG. 2 is a CoZn-MOF/NiCo example 2 2 O 4 Scanning electron microscope picture of @ CNTs/rGO composite electrode material;
FIG. 3 is a CoZn-MOF/NiCo example 2 2 O 4 Transmission electron microscope photo of @ CNTs/rGO composite electrode material;
FIG. 4 is a diagram of CoZn-MOF/NiCo prepared in example 2 2 O 4 The cyclic voltammogram of the @ CNTs/rGO composite electrode material;
FIG. 5 is a CoZn-MOF/NiCo sample prepared in example 2 2 O 4 Constant current charge and discharge curve diagram of @ CNTs/rGO composite electrode material.
Detailed Description
The invention is further described with reference to specific examples.
The reagents used in the following examples are all commercially available as cobalt nitrate hexahydrate (Co (NO) 3 ) 2 ·6H 2 O), nickel nitrate hexahydrate (Ni (NO) 3 ) 2 ·6H 2 O), zinc nitrate hexahydrate (Zn (NO) 3 ) 2 ·6H 2 O), ammonium fluoride (NH) 4 F) Urea (CH) 4 N 2 O), anhydrous ethanol(C 2 H 5 OH) and potassium hydroxide (KOH), available from national chemical group, ltd; 2-methylimidazole (C) 4 H 6 N 2 ) 98% was purchased from aladine; carbon Nanotubes (CNTs) were purchased from qian su xian nano materials science and technology ltd.
CoZn-MOF/NiCo prepared by the invention 2 O 4 The @ CNTs/rGO composite film electrode material is used for carrying out structural analysis and performance analysis on a product by utilizing an X-ray diffractometer (XRD), a CHI760E electrochemical workstation and other instruments so as to evaluate the electrochemical activity of the product.
Example 1
MOF-derived CoZn-MOF/NiCo 2 O 4 The preparation method of the composite electrode material with the nano-particles growing on the carbon cloth comprises the following steps:
step 1, preparing graphene oxide GO dispersion liquid with the density of 0.2 mg/mL. And uniformly mixing and stirring the carbon nano tube and the GO dispersion liquid according to the volume ratio of 1:500, and performing vacuum filtration to obtain the CNTs/GO membrane. 0.559g of Co (NO) 3 ) 2 ·6H 2 O、0.279g Ni(NO 3 ) 2 ·6H 2 O, 0.291g Urea and 0.059g NH 4 F is added into 20mL of deionized water, and then the prepared solution is mixed and stirred uniformly at room temperature. Then transferring the mixed solution into a reaction kettle, immersing the mixed solution into a dried graphene and carbon nanotube (CNTs/GO) film, keeping the temperature of 110 ℃ for 4 hours, naturally cooling to room temperature, taking out the film, alternately washing with deionized water and ethanol, and drying to obtain NiCo 2 O 4 @ CNTs/rGO composite films;
step 2, weighing 0.59g Co (NO) 3 ) 2 ·6H 2 O and 0.30g Zn (NO) 3 ) 2 ·6H 2 O was dissolved in 80mL of deionized water and mixed well by ultrasonic dissolution. 1.3g of 2-methylimidazole is weighed and dissolved in 40mL of deionized water, and the solution is fully dissolved by ultrasonic. And adding the 2-methylimidazole solution into the mixed nitrate solution to obtain a CoZn-MOF suspension. Mixing NiCo with a solvent 2 O 4 Immersing the @ CNTs/rGO composite film into a CoZn-MOF suspension at room temperature, washing the sample for 3-4 times by using absolute ethyl alcohol and deionized water alternately, and drying at 60 ℃ to obtain the CoZn-MOF/NiCo 2 O 4 @ CNTs/rGO complexFilm of NiCo therein 2 O 4 The immersion time of the @ CNTs/rGO composite film is 1h;
step 3, heating the CoZn-MOF/NiCo in a muffle furnace to 350 ℃ at a heating rate of 2 ℃/min, and performing temperature control on the CoZn-MOF/NiCo 2 O 4 The @ CNTs/rGO film was annealed for 2 hours to obtain the corresponding oxide.
Example 2
MOF-derived CoZn-MOF/NiCo 2 O 4 The preparation method of the composite electrode material with the nano particles growing on the carbon cloth comprises the following steps:
step 1, preparing graphene oxide GO dispersion liquid with the density of 0.2 mg/mL. And uniformly mixing and stirring the carbon nano tube and the GO dispersion liquid according to the volume ratio of 1:500, and performing vacuum filtration to obtain a CNTs/GO membrane. 0.663g of Co (NO) 3 ) 2 ·6H 2 O、0.279g Ni(NO 3 ) 2 ·6H 2 O, 0.291g Urea and 0.059g NH 4 F is added into 20mL of deionized water, and then the prepared solution is mixed and stirred uniformly at room temperature. Then transferring the mixed solution into a reaction kettle, immersing the mixed solution into a dried graphene and carbon nanotube (CNTs/GO) film, keeping the temperature of 110 ℃ for 4 hours, naturally cooling to room temperature, taking out the film, alternately washing with deionized water and ethanol, and drying to obtain NiCo 2 O 4 @ CNTs/rGO composite films;
step 2, weighing 0.63g Co (NO) 3 ) 2 ·6H 2 O and 0.30g Zn (NO) 3 ) 2 ·6H 2 O was dissolved in 80mL of deionized water and mixed well by ultrasonic dissolution. 1.4g of 2-methylimidazole was weighed and dissolved in 40mL of deionized water, and the solution was dissolved sufficiently by ultrasonic. And adding a 2-methylimidazole solution into the mixed nitrate solution to obtain a CoZn-MOF suspension. Mixing NiCo 2 O 4 Immersing the @ CNTs/rGO composite film into a CoZn-MOF suspension at room temperature, washing the sample for 3-4 times by using absolute ethyl alcohol and deionized water alternately, and drying at 60 ℃ to obtain the CoZn-MOF/NiCo 2 O 4 @ CNTs/rGO composite membranes, of which NiCo 2 O 4 The soaking time of the @ CNTs/rGO composite film is 1h;
step 3, heating the temperature to 350 ℃ in a muffle furnace at a heating rate of 3 ℃/min, and carrying out CoZn-MOF/NiCo treatment at the temperature 2 O 4 The @ CNTs/rGO film was annealed for 2 hours to obtain the corresponding oxide.
CoZn-MOF/NiCo 2 O 4 Characterization and analysis of @ CNTs/rGO composite electrode material:
as shown in FIG. 1, it can be seen that there is NiCo 2 S 4 And ZnCo 2 S 4 The diffraction peak of (A) has no other impurity phase, which shows that the CoZn-MOF/NiCo is successfully prepared 2 O 4 @ CNTs/rGO films.
As shown in FIG. 2, coZn-MOF/NiCo can be seen 2 O 4 The nanoparticles are uniformly grown in situ on the graphene and the carbon nanotubes to form a composite structure.
As shown in FIG. 3, coZn-MOF/NiCo can be seen 2 O 4 The nano particles are nano-cluster-shaped particles formed by nano sheets and successfully attached to the graphene and the carbon nano tube to form a composite nano structure.
Example 3
MOF-derived CoZn-MOF/NiCo 2 O 4 The preparation method of the composite electrode material with the nano particles growing on the carbon cloth comprises the following steps:
step 1, preparing graphene oxide GO dispersion liquid with the density of 0.2 mg/mL. Mixing carbon nanotubes and the GO dispersion liquid in a volume ratio of 1:500, and obtaining a CNTs/GO membrane through vacuum filtration. 0.559g of Co (NO) 3 ) 2 ·6H 2 O、0.421g Ni(NO 3 ) 2 ·6H 2 O, 0.291g Urea and 0.059g NH 4 F is added into 20mL of deionized water, and then the prepared solution is mixed and stirred uniformly at room temperature. Then transferring the mixed solution into a reaction kettle, immersing the mixed solution into a dried graphene and carbon nanotube (CNTs/GO) film, keeping the temperature of 110 ℃ for 4 hours, naturally cooling to room temperature, taking out the film, alternately washing with deionized water and ethanol, and drying to obtain NiCo 2 O 4 @ CNTs/rGO composite films;
step 2, weighing 0.59g Co (NO) 3 ) 2 ·6H 2 O and 0.48g Zn (NO) 3 ) 2 ·6H 2 O was dissolved in 80mL of deionized water and mixed well by ultrasonic dissolution. Weighing 1.4g 2-methylimidazolium solutionThe solution is fully dissolved in 40mL of deionized water by ultrasonic. And adding the 2-methylimidazole solution into the mixed nitrate solution to obtain a CoZn-MOF suspension. Mixing NiCo 2 O 4 Immersing the @ CNTs/rGO composite film into a CoZn-MOF suspension at room temperature, finally alternately washing the sample with absolute ethyl alcohol and deionized water for 3 to 4 times, and drying at 60 ℃ to obtain the CoZn-MOF/NiCo composite film 2 O 4 @ CNTs/rGO composite membranes, of which NiCo 2 O 4 The soaking time of the @ CNTs/rGO composite film is 1h;
step 3, heating the temperature to 350 ℃ in a muffle furnace at a heating rate of 4 ℃/min, and carrying out CoZn-MOF/NiCo treatment at the temperature 2 O 4 The @ CNTs/rGO film was annealed for 2 hours to obtain the corresponding oxide.
Example 4
MOF-derived CoZn-MOF/NiCo 2 O 4 The preparation method of the composite electrode material with the nano-particles growing on the carbon cloth comprises the following steps:
step 1, preparing graphene oxide GO dispersion liquid with the density of 0.2 mg/mL. Mixing carbon nano tubes and the GO dispersion liquid according to a volume ratio of 1:500, and obtaining a CNTs/GO membrane through vacuum filtration. 0.559g of Co (NO) 3 ) 2 ·6H 2 O、0.279g Ni(NO 3 ) 2 ·6H 2 O, 0.347g urea and 0.059g NH 4 F is added into 20mL of deionized water, and then the prepared solution is mixed and stirred uniformly at room temperature. Then transferring the mixed solution into a reaction kettle, immersing the mixed solution into a dried graphene and carbon nanotube (CNTs/GO) film, keeping the temperature of 110 ℃ for 4 hours, naturally cooling to room temperature, taking out the film, alternately washing with deionized water and ethanol, and drying to obtain NiCo 2 O 4 @ CNTs/rGO composite films;
step 2, weighing 0.63g Co (NO) 3 ) 2 ·6H 2 O and 0.48g Zn (NO) 3 ) 2 ·6H 2 O was dissolved in 80mL of deionized water and mixed well by ultrasonic dissolution. 1.4g of 2-methylimidazole was weighed and dissolved in 40mL of deionized water, and the solution was dissolved sufficiently by ultrasonic. And adding a 2-methylimidazole solution into the mixed nitrate solution to obtain a CoZn-MOF suspension. Mixing NiCo 2 O 4 @ CNTs/rGO composite film immersed in CoZn-MOF at room temperatureIn the suspension, finally, the sample is washed 3 to 4 times by using anhydrous ethanol and deionized water alternately and dried at 60 ℃ to obtain CoZn-MOF/NiCo 2 O 4 @ CNTs/rGO composite membranes, of which NiCo 2 O 4 The soaking time of the @ CNTs/rGO composite film is 1h;
step 3, heating the CoZn-MOF/NiCo in a muffle furnace to 350 ℃ at a heating rate of 5 ℃/min, and heating the CoZn-MOF/NiCo at the temperature 2 O 4 The @ CNTs/rGO film was annealed for 2 hours to obtain the corresponding oxide.
Example 5
MOF-derived CoZn-MOF/NiCo 2 O 4 The preparation method of the composite electrode material with the nano particles growing on the carbon cloth comprises the following steps:
step 1, preparing graphene oxide GO dispersion liquid with the density of 0.2 mg/mL. And uniformly mixing and stirring the carbon nano tube and the GO dispersion liquid according to the volume ratio of 1:500, and performing vacuum filtration to obtain the CNTs/GO membrane. 0.559g of Co (NO) 3 ) 2 ·6H 2 O、0.279g Ni(NO 3 ) 2 ·6H 2 O, 0.291g Urea and 0.071g NH 4 F is added into 20mL of deionized water, and then the prepared solution is mixed and stirred uniformly at room temperature. Then transferring the mixed solution into a reaction kettle, immersing the mixed solution into a dried graphene and carbon nanotube (CNTs/GO) film, keeping the temperature of 110 ℃ for 4 hours, naturally cooling to room temperature, taking out the film, alternately washing with deionized water and ethanol, and drying to obtain NiCo 2 O 4 @ CNTs/rGO composite films;
step 2, weighing 0.63g Co (NO) 3 ) 2 ·6H 2 O and 0.30g Zn (NO) 3 ) 2 ·6H 2 O was dissolved in 80mL of deionized water and mixed well by ultrasonic dissolution. 1.4g2-methylimidazole is weighed and dissolved in 40mL of deionized water, and the solution is fully dissolved by ultrasonic. And adding the 2-methylimidazole solution into the mixed nitrate solution to obtain a CoZn-MOF suspension. Mixing NiCo with a solvent 2 O 4 Immersing the @ CNTs/rGO composite film into a CoZn-MOF suspension at room temperature, finally alternately washing the sample with absolute ethyl alcohol and deionized water for 3 to 4 times, and drying at 60 ℃ to obtain the CoZn-MOF/NiCo composite film 2 O 4 @ CNTs/rGO composite membranes, of which NiCo 2 O 4 @ CNTs/rGO composite sheetThe membrane immersion time is 2h;
step 3, heating the temperature of the muffle furnace to 350 ℃ at a heating rate of 3 ℃/min, and carrying out the temperature control on the CoZn-MOF/NiCo at the temperature 2 O 4 The @ CNTs/rGO film was annealed for 2 hours to obtain the corresponding oxide.
Example 6
MOF-derived CoZn-MOF/NiCo 2 O 4 The preparation method of the composite electrode material with the nano-particles growing on the carbon cloth comprises the following steps:
step 1, preparing graphene oxide GO dispersion liquid with the density of 0.2 mg/mL. And uniformly mixing and stirring the carbon nano tube and the GO dispersion liquid according to the volume ratio of 1:500, and performing vacuum filtration to obtain a CNTs/GO membrane. 0.663g of Co (NO) 3 ) 2 ·6H 2 O、0.279g Ni(NO 3 ) 2 ·6H 2 O, 0.291g Urea and 0.059g NH 4 F is added into 20mL of deionized water, and then the prepared solution is mixed and stirred uniformly at room temperature. Then transferring the mixed solution into a reaction kettle, immersing the mixed solution into a dried graphene and carbon nanotube (CNTs/GO) film, keeping the temperature of 110 ℃ for 4 hours, naturally cooling to room temperature, taking out the film, alternately washing with deionized water and ethanol, and drying to obtain NiCo 2 O 4 @ CNTs/rGO composite films;
step 2, weighing 0.59g Co (NO) 3 ) 2 ·6H 2 O and 0.48g Zn (NO) 3 ) 2 ·6H 2 O was dissolved in 80mL of deionized water and mixed well by ultrasonic dissolution. 1.4g of 2-methylimidazole is weighed and dissolved in 40mL of deionized water, and the solution is fully dissolved by ultrasonic. And adding the 2-methylimidazole solution into the mixed nitrate solution to obtain a CoZn-MOF suspension. Mixing NiCo 2 O 4 Immersing the @ CNTs/rGO composite film into a CoZn-MOF suspension at room temperature, finally alternately washing the sample with absolute ethyl alcohol and deionized water for 3 to 4 times, and drying at 60 ℃ to obtain the CoZn-MOF/NiCo composite film 2 O 4 @ CNTs/rGO composite membranes, of which NiCo 2 O 4 The immersion time of the @ CNTs/rGO composite film is 2h;
step 3, heating the temperature of the muffle furnace to 350 ℃ at a heating rate of 4 ℃/min, and carrying out the temperature control on the CoZn-MOF/NiCo at the temperature 2 O 4 Annealing @ CNTs/rGO film for 2 hours to obtainThe corresponding oxide.
Example 7
MOF-derived CoZn-MOF/NiCo 2 O 4 The preparation method of the composite electrode material with the nano-particles growing on the carbon cloth comprises the following steps:
step 1, preparing graphene oxide GO dispersion liquid with the density of 0.2 mg/mL. And uniformly mixing and stirring the carbon nano tube and the GO dispersion liquid according to the volume ratio of 1:500, and performing vacuum filtration to obtain a CNTs/GO membrane. 0.559g of Co (NO) 3 ) 2 ·6H 2 O、0.421g Ni(NO 3 ) 2 ·6H 2 O, 0.291g Urea and 0.059g NH 4 F is added into 20mL of deionized water, and then the prepared solution is mixed and stirred uniformly at room temperature. Then transferring the mixed solution into a reaction kettle, immersing the mixed solution into a dried graphene and carbon nanotube (CNTs/GO) film, keeping the temperature of 110 ℃ for 4 hours, naturally cooling to room temperature, taking out the film, alternately washing with deionized water and ethanol, and drying to obtain NiCo 2 O 4 @ CNTs/rGO composite films;
step 2, weighing 0.63g Co (NO) 3 ) 2 ·6H 2 O and 0.48g Zn (NO) 3 ) 2 ·6H 2 O was dissolved in 80mL of deionized water and mixed well by ultrasonic dissolution. 1.4g of 2-methylimidazole was weighed and dissolved in 40mL of deionized water, and the solution was dissolved sufficiently by ultrasonic. And adding the 2-methylimidazole solution into the mixed nitrate solution to obtain a CoZn-MOF suspension. Mixing NiCo 2 O 4 Immersing the @ CNTs/rGO composite film into a CoZn-MOF suspension at room temperature, washing the sample for 3-4 times by using absolute ethyl alcohol and deionized water alternately, and drying at 60 ℃ to obtain the CoZn-MOF/NiCo 2 O 4 @ CNTs/rGO composite membranes, of which NiCo 2 O 4 The soaking time of the @ CNTs/rGO composite film is 2h;
step 3, heating the temperature to 350 ℃ in a muffle furnace at a heating rate of 5 ℃/min, and carrying out CoZn-MOF/NiCo treatment at the temperature 2 O 4 The @ CNTs/rGO film was annealed for 2 hours to obtain the corresponding oxide.
Example 8
MOF-derived CoZn-MOF/NiCo 2 O 4 Preparation of composite electrode material with nano-particles grown on carbon clothThe method comprises the following steps:
step 1, preparing graphene oxide GO dispersion liquid with the density of 0.2 mg/mL. And uniformly mixing and stirring the carbon nano tube and the GO dispersion liquid according to the volume ratio of 1:500, and performing vacuum filtration to obtain the CNTs/GO membrane. 0.559g of Co (NO) 3 ) 2 ·6H 2 O、0.279g Ni(NO 3 ) 2 ·6H 2 O, 0.347g urea and 0.059g NH 4 F is added into 20mL of deionized water, and then the prepared solution is mixed and stirred uniformly at room temperature. Then transferring the mixed solution into a reaction kettle, immersing the mixed solution into a dried graphene and carbon nanotube (CNTs/GO) film, keeping the temperature at 110 ℃ for 4 hours, naturally cooling to room temperature, taking out the film, alternately washing the film with deionized water and ethanol, and drying the film to obtain NiCo 2 O 4 @ CNTs/rGO composite films;
step 2, weighing 0.63g Co (NO) 3 ) 2 ·6H 2 O and 0.30g Zn (NO) 3 ) 2 ·6H 2 O was dissolved in 80mL of deionized water and mixed well by ultrasonic dissolution. 1.4g of 2-methylimidazole was weighed and dissolved in 40mL of deionized water, and the solution was dissolved sufficiently by ultrasonic. And adding a 2-methylimidazole solution into the mixed nitrate solution to obtain a CoZn-MOF suspension. Mixing NiCo with a solvent 2 O 4 Immersing the @ CNTs/rGO composite film into a CoZn-MOF suspension at room temperature, finally alternately washing the sample with absolute ethyl alcohol and deionized water for 3 to 4 times, and drying at 60 ℃ to obtain the CoZn-MOF/NiCo composite film 2 O 4 @ CNTs/rGO composite membranes, of which NiCo 2 O 4 The soaking time of the @ CNTs/rGO composite film is 3h;
step 3, heating the temperature of the muffle furnace to 350 ℃ at a heating rate of 3 ℃/min, and carrying out the temperature control on the CoZn-MOF/NiCo at the temperature 2 O 4 The @ CNTs/rGO film was annealed for 2 hours to obtain the corresponding oxide.
Example 9
MOF-derived CoZn-MOF/NiCo 2 O 4 The preparation method of the composite electrode material with the nano-particles growing on the carbon cloth comprises the following steps:
step 1, preparing graphene oxide GO dispersion liquid with the density of 0.2 mg/mL. Mixing carbon nanotube and GO dispersion at a volume ratio of 1:500, stirring, and vacuum filtering to obtain a sheetCNTs/GO membranes. 0.559g of Co (NO) 3 ) 2 ·6H 2 O、0.279g Ni(NO 3 ) 2 ·6H 2 O, 0.291g Urea and 0.071g NH 4 F is added into 20mL of deionized water, and then the prepared solution is mixed and stirred uniformly at room temperature. Then transferring the mixed solution into a reaction kettle, immersing the mixed solution into a dried graphene and carbon nanotube (CNTs/GO) film, keeping the temperature of 110 ℃ for 4 hours, naturally cooling to room temperature, taking out the film, alternately washing with deionized water and ethanol, and drying to obtain NiCo 2 O 4 @ CNTs/rGO composite films;
step 2, weighing 0.59g Co (NO) 3 ) 2 ·6H 2 O and 0.48g Zn (NO) 3 ) 2 ·6H 2 O was dissolved in 80mL of deionized water and mixed well by ultrasonic dissolution. 1.4g of 2-methylimidazole is weighed and dissolved in 40mL of deionized water, and the solution is fully dissolved by ultrasonic. And adding the 2-methylimidazole solution into the mixed nitrate solution to obtain a CoZn-MOF suspension. Mixing NiCo with a solvent 2 O 4 Immersing the @ CNTs/rGO composite film into a CoZn-MOF suspension at room temperature, washing the sample for 3-4 times by using absolute ethyl alcohol and deionized water alternately, and drying at 60 ℃ to obtain the CoZn-MOF/NiCo 2 O 4 @ CNTs/rGO composite membranes, of which NiCo 2 O 4 The soaking time of the @ CNTs/rGO composite film is 3h;
step 3, heating the temperature of the muffle furnace to 350 ℃ at a heating rate of 4 ℃/min, and carrying out the temperature control on the CoZn-MOF/NiCo at the temperature 2 O 4 The @ CNTs/rGO film was annealed for 2 hours to obtain the corresponding oxide.
Example 10
MOF-derived CoZn-MOF/NiCo 2 O 4 The preparation method of the composite electrode material with the nano-particles growing on the carbon cloth comprises the following steps:
step 1, preparing graphene oxide GO dispersion liquid with the density of 0.2 mg/mL. Mixing carbon nanotubes and the GO dispersion liquid in a volume ratio of 1:500, and obtaining a CNTs/GO membrane through vacuum filtration. 0.663g of Co (NO) 3 ) 2 ·6H 2 O、0.279g Ni(NO 3 ) 2 ·6H 2 O, 0.291g Urea and 0.059g NH 4 F is added into 20mL of deionized water, and then the mixture is preparedThe solution of (2) was mixed and stirred at room temperature. Then transferring the mixed solution into a reaction kettle, immersing the mixed solution into a dried graphene and carbon nanotube (CNTs/GO) film, keeping the temperature of 110 ℃ for 4 hours, naturally cooling to room temperature, taking out the film, alternately washing with deionized water and ethanol, and drying to obtain NiCo 2 O 4 @ CNTs/rGO composite films;
step 2, weighing 0.63g Co (NO) 3 ) 2 ·6H 2 O and 0.48g Zn (NO) 3 ) 2 ·6H 2 O was dissolved in 80mL of deionized water and mixed well by ultrasonic dissolution. 1.4g of 2-methylimidazole was weighed and dissolved in 40mL of deionized water, and the solution was dissolved sufficiently by ultrasonic. And adding the 2-methylimidazole solution into the mixed nitrate solution to obtain a CoZn-MOF suspension. Mixing NiCo with a solvent 2 O 4 Immersing the @ CNTs/rGO composite film into a CoZn-MOF suspension at room temperature, finally alternately washing the sample with absolute ethyl alcohol and deionized water for 3 to 4 times, and drying at 60 ℃ to obtain the CoZn-MOF/NiCo composite film 2 O 4 @ CNTs/rGO composite membranes, of which NiCo 2 O 4 The soaking time of the @ CNTs/rGO composite film is 3h;
step 3, heating the temperature to 350 ℃ in a muffle furnace at a heating rate of 5 ℃/min, and carrying out CoZn-MOF/NiCo treatment at the temperature 2 O 4 The @ CNTs/rG0 thin film was annealed for 2 hours to obtain the corresponding oxide.
Example 11
CoZn-MOF/NiCo prepared in example 2 2 O 4 The @ CNTs/rGO composite electrode material is used as a positive electrode material, 6mol/L KOH is used as electrolyte, activated carbon, conductive carbon black and a binder Polytetrafluoroethylene (PTFE) are uniformly mixed and dispersed in absolute ethyl alcohol according to the mass ratio of 8:1, then the mixture is coated on foamed nickel, and the foamed nickel is dried and pressed into sheets to prepare the electrode sheet serving as the negative electrode material of the supercapacitor.
Performing electrochemical performance tests such as Cyclic Voltammetry (CV) and constant current charging and discharging in a two-electrode system, and calculating corresponding energy density and power density to evaluate the prepared CoZn-MOF/NiCo 2 O 4 Electrochemical properties of @ CNTs/rGO composite films. Wherein the voltage range of the Cyclic Voltammetry (CV) test is 0-1.7V, and the scanning speed is 2, 5, 10, 20, 50 and 100mV/s, voltage range of constant current charge and discharge test is 0-1.7V, and current density is 1, 2, 3, 5, 8 and 10A/g.
As shown in FIG. 4, it can be seen from the CV curve that the larger the sweep rate of the synthesized CoZn-MOF/NiCo2O4@ CNTs/rGO composite electrode material, the larger the integrated area.
As shown in FIG. 5, it can be seen from the GCD curve that the synthesized CoZn-MOF/NiCo2O4@ CNTs/rGO composite electrode material is at 1Ag -1 Specific capacitance of time is 1708Fg -1 。
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present invention or directly or indirectly applied to other related technical fields are included in the scope of the present invention.

Claims (8)

1. CoZn-MOF/NiCo 2 O 4 A preparation method of a @ CNTs/rGO composite electrode material is characterized by comprising the following steps:
1) Uniformly mixing and stirring the carbon nano tube and GO dispersion liquid, and performing vacuum filtration to obtain a CNTs/GO membrane; adding Co (NO) separately 3 ) 2 ·6H 2 O、Ni(NO 3 ) 2 ·6H 2 O, urea and NH 4 F, adding the mixed solution into deionized water, and then uniformly stirring the prepared solution at room temperature to prepare a mixed solution, co (NO) 3 ) 2 ·6H 2 O、Ni(NO 3 ) 2 ·6H 2 O, urea and NH 4 The mass ratio of F is 0.5-0.7; urea and NH 4 The molar concentration ratio of F is 0.20-0.30; transferring the mixed solution into a reaction kettle, immersing the CNTs/GO membrane into the mixed solution, keeping the temperature at 110 ℃ for 4 hours, naturally cooling to room temperature, taking out the solution, alternately washing the solution with deionized water and ethanol, and drying the solution to obtain NiCo 2 O 4 @ CNTs/rGO composite films;
2) Preparation of Co (NO) 3 ) 2 ·6H 2 O、Zn(NO 3 ) 2 ∙6H 2 Fully dissolving O and 2-methylimidazole solution by ultrasonic, and uniformly mixing and stirring to obtain a CoZn-MOF suspension; will be described inNiCo of (5) 2 O 4 The @ CNTs/rGO composite film is immersed in the CoZn-MOF suspension for 0.5 h-6 h to obtain the CoZn-MOF/NiCo 2 O 4 @ CNTs/rGO composite electrode materials; the Co (NO) 3 ) 2 ·6H 2 O and Zn (NO) 3 ) 2 ∙6H 2 The mass ratio of O is 0.5-0.7; the molar concentration of the 2-methylimidazole solution is 0.39-0.45mol/L;
3) For the CoZn-MOF/NiCo prepared in the step 2) 2 O 4 And carrying out annealing treatment on the @ CNTs/rGO composite electrode material, wherein the annealing temperature is 350 ℃, and the annealing time is 2h.
2. The CoZn-MOF/NiCo of claim 1 2 O 4 The preparation method of the @ CNTs/rGO composite electrode material is characterized in that in the step 1), the concentration of the GO dispersion liquid is 0.2mg/mL; the carbon nano tube and GO dispersion liquid are uniformly mixed and stirred according to the volume ratio of 1.
3. The CoZn-MOF/NiCo of claim 1 2 O 4 The preparation method of the @ CNTs/rGO composite electrode material is characterized in that in the step 1), ni (NO) 3 ) 2 ·6H 2 O、Co(NO 3 ) 2 ·6H 2 O, urea and NH 4 The volume ratio of the solution F is 1.
4. CoZn-MOF/NiCo according to claim 1 2 O 4 The preparation method of the @ CNTs/rGO composite electrode material is characterized in that in the step 2), co (NO) is used 3 ) 2 ·6H 2 O and Zn (NO) 3 ) 2 ∙6H 2 Mixing and stirring the O solution uniformly according to a volume ratio of 1; the mixed nitrate solution and the 2-methylimidazole solution are mixed and stirred uniformly again according to the volume ratio of 2; adding the NiCo 2 O 4 The @ CNTs/rGO composite film is immersed in the CoZn-MOF suspension for 1h.
5. CoZn-MOF/NiCo according to claim 1 2 O 4 The preparation method of the @ CNTs/rGO composite electrode material is characterized in that in the step 3), the material is heated to the annealing temperature of 350 ℃ at the heating rate of 2-5 ℃/min.
6. CoZn-MOF/NiCo prepared by the method of any one of claims 1 to 5 2 O 4 @ CNTs/rGO composite electrode materials.
7. The CoZn-MOF/NiCo of claim 6 2 O 4 The application of the @ CNTs/rGO composite electrode material as a supercapacitor material.
8. CoZn-MOF/NiCo according to claim 7 2 O 4 The application of the @ CNTs/rGO composite electrode material as a supercapacitor material is characterized in that CoZn-MOF/NiCo 2 O 4 The @ CNTs/rGO composite electrode material is used as a positive electrode material, 6mol/L KOH is used as electrolyte, activated carbon, conductive carbon black and polytetrafluoroethylene are uniformly mixed and dispersed in absolute ethyl alcohol according to the mass ratio of 8.
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