CN111292969A - Co2V2O7Hollow nanocage/graphene composite material, preparation method thereof and application of composite material in super capacitor - Google Patents
Co2V2O7Hollow nanocage/graphene composite material, preparation method thereof and application of composite material in super capacitor Download PDFInfo
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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
- H01G11/84—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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- 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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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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
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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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
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- 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
- Y02E60/13—Energy storage using capacitors
Abstract
The invention relates to Co2V2O7A hollow nanocage/graphene composite material, a preparation method thereof and application of the composite material in a super capacitor are provided. The method comprises the following steps: 1) uniformly growing cobalt-based MOF (ZIF-67) on the surface of graphene by utilizing the adsorption effect of graphene oxide on metal ions; 2) converting ZIF-67 grown on graphene into Co consisting of nanoparticles using ion exchange reaction2V2O7Hollow nanocage to obtain Co2V2O7A hollow nanocage/graphene composite material. The invention grows ZIF-67 on graphene, andin-situ synthesis of ultrahigh-performance Co serving as precursor2V2O7The hollow nano cage/graphene electrode material is used for constructing an electrode material of a high-performance super capacitor, and shows high mass specific capacitance and excellent cycling stability.
Description
Technical Field
The invention belongs to the field of super capacitors, and particularly relates to Co2V2O7Preparation of a hollow nano cage/graphene composite material and application of the composite material in a super capacitor.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
The super capacitor is a novel energy storage device between a traditional capacitor and a secondary battery (a lithium battery, a nickel-metal hydride battery and the like), and has the advantages of high power density, short charging and discharging time, long cycle life, wide working temperature, small pollution and the like. Generally, supercapacitors can be divided into two distinct categories depending on the difference in energy storage mechanism: electrochemical double layer capacitors and pseudocapacitors. Electrochemical double layer capacitor energy storage is based on nanoscale charge stratification at the electrochemical interface of the electrode and electrolyte composition, whereas pseudocapacitors can store energy through additional reversible redox reactions with higher capacitance and energy density.
Among many pseudocapacitance materials, transition metal oxides are widely concerned due to the characteristics that the valence state of the element is adjustable, the transition metal oxide is stable and does not undergo phase change, and rapid and reversible redox reaction can occur. Among many transition metal oxides, binary metal oxides have richer redox states and higher conductivity than unit metal oxides, and thus are hot spots for research on electrode materials of supercapacitors. When the cobalt-vanadium bimetallic oxide is used in the field of super capacitors, the cobalt-vanadium bimetallic oxide has good cycle stability, but the inventor finds that: the existing cobalt-vanadium bimetallic oxide electrode material still has the defects of low conductivity, low specific capacitance and the like due to the defects of the surrounding structure or the component design.
Disclosure of Invention
The invention aims to solve the problems of cobalt-vanadium bimetallic oxide and provides Co2V2O7A preparation method of a hollow nano cage/graphene composite electrode material aims to solve the problem that the conductivity of a cobalt-vanadium bimetallic oxide is improved to be very specific capacitance under the advantage of long cycle life.
In order to achieve the technical purpose, the first aspect of the invention adopts the following technical scheme:
co2V2O7The preparation method of the hollow nanocage/graphene composite material comprises the following steps:
adding cobalt salt into the dispersion liquid of the graphene oxide, and uniformly mixing to obtain a solution A;
mixing the solution A with an alcoholic solution of 2-methylimidazole, and standing to form ZIF-67/graphene;
carrying out ion exchange reaction on ZIF-67/graphene and metavanadate to form Co2V2O7A hollow nanocage/graphene composite material.
At present, many hollow nano cage/graphene composite materials need to be subjected to high-temperature treatment to obtain oxides, the oxides can be directly synthesized by the method, high-temperature treatment is not needed, and the method is simpler and energy-saving.
Another aspect of the present invention provides Co prepared by the above method2V2O7A hollow nanocage/graphene composite material.
A third aspect of the present invention provides the above-mentioned Co2V2O7The application of the hollow nano cage/graphene composite material in preparing the super capacitor.
The principle of the invention is as follows: in a reaction system, divalent cobalt ions are captured by rich oxygen-containing groups on the surface of oxidized graphene and are uniformly adsorbed on the surface of the oxidized graphene,and reacting with 2-methylimidazole to generate ZIF-67 on the surface of graphene. In an alkaline environment, ZIF-67 on the surface of graphene is subjected to ion exchange with metavanadate ions, and Co is generated on the surface of ZIF-672V2O7As the reaction proceeds, ZIF-67 is completely decomposed and converted into Co2V2O7Hollow nanocages, thereby forming Co2V2O7Hollow nanocages/graphene.
The invention has the beneficial effects that:
(1) the preparation method is simple, and long-time high-temperature treatment is not needed;
(2) co of the invention2V2O7Uniformly compounding the hollow nano cage and the graphene;
(3) the invention has higher specific capacitance and excellent cycling stability.
(4) The operation method is simple, low in cost, universal and easy for large-scale production.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application.
FIG. 1 is a scanning electron micrograph of ZIF-67/graphene of example 1.
FIG. 2 shows Co in example 12V2O7Scanning electron microscopy of hollow nanocages/graphene.
FIG. 3 shows Co in example 12V2O7Transmission electron microscopy of hollow nanocages/graphene.
FIG. 4 shows Co in example 12V2O7And a charge-discharge curve diagram of the hollow nano cage/graphene under different current densities.
FIG. 5 shows Co in example 12V2O7Cycle performance diagram of hollow nanocages/graphene.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As introduced in the background art, the problems of low conductivity and low specific capacitance exist in the current cobalt-vanadium double-metal oxide electrode material. Therefore, the present invention provides a Co2V2O7The preparation method of the hollow nano cage/graphene composite material comprises the steps of dispersing graphene oxide into a certain amount of methanol, adding a certain amount of cobalt salt and 2-methylimidazole methanol solution, and reacting for a period of time. Carrying out ion exchange reaction on the obtained sample and metavanadate for a period of time to obtain Co2V2O7A hollow nanocage/graphene composite material. The method comprises the following specific steps:
step (1): preparation of ZIF-67/graphene
Firstly, ultrasonically dispersing a certain amount of graphene oxide powder in methanol, adding cobalt salt, and stirring to obtain a solution A. Next, a certain amount of 2-methylimidazole was dissolved in the same volume of methanol as that of the solution A to obtain a solution B. And finally, mixing the solution A, B, and standing for 6-24h at room temperature to obtain ZIF-67/graphene. The improved synthesis method improves the electrochemical performance, particularly the conductivity, of the cobalt-vanadium bimetallic oxide under the advantage of long cycle life.
The graphene oxide is prepared by a hummer method and contains rich oxygen-containing groups, and the mass ratio of the cobalt salt to the 2-methylimidazole is 1:2-1: 8.
And adding 10-30mg of graphene oxide powder into 50mL of methanol in the solution A.
In the solution B, 0.4-1.2mmol of 2-methylimidazole is added to 50mL of methanol.
Step (2): preparation of Co2V2O7Hollow nanocage/graphene composite material
And ultrasonically dispersing the ZIF-67/graphene prepared in the first step into an ethanol solution to obtain a solution C. And dissolving metavanadate in the mixed solution of ammonia water/water to obtain a solution D. Slowly adding the solution C into the solution D, stirring, and keeping the temperature at 60-80 ℃ for 0.5-2h to obtain Co2V2O7Hollow nanocages/graphene.
And adding 60-100mg of ZIF-67/graphene into each 20mL of ethanol in the solution C.
In the solution D, the volume ratio of ammonia water to water is 5:15-1: 19.
The present invention is described in further detail below with reference to specific examples, which are intended to be illustrative of the invention and not limiting.
Example 1:
step (1): preparation of ZIF-67/graphene
Ultrasonically dispersing 25mg of graphene oxide powder in 50mL of methanol, adding 2mmol of cobalt nitrate, and stirring to obtain a solution A for later use.
8mmol of 2-methylimidazole were dissolved in 50mL of methanol to obtain a solution B for use.
And slowly adding the solution B into the solution A, stirring for 5 minutes, and standing at room temperature for 24 hours to obtain ZIF-67/graphene for later use.
Step (2): preparation of Co2V2O7Hollow nanocage/graphene composite material
Ultrasonically dispersing the ZIF-67/graphene prepared in the step (1) into 20mL of ethanol solution to obtain a solution C for later use.
1.6mmol of ammonium metavanadate is dissolved in 20ml of an ammonia water/water mixed solution to obtain a solution D for later use.
Slowly adding the solution C into the solution DStirring, and keeping the temperature at 80 ℃ for 1h to obtain Co2V2O7Hollow nanocages/graphene.
And (3) characterization of micro morphology:
the morphology of the ZIF-67/graphene prepared in the step (1) is shown in FIG. 1, and it can be seen that the ZIF-67 uniformly grows on the graphene. Direct growth on graphene can reduce the aggregation of ZIF-67 and improve conductivity.
Co prepared in step (2)2V2O7As shown in FIGS. 2 and 3, ZIF-67 on the surface of graphene in FIG. 1 is converted into Co2V2O7A hollow nanocage, and the nanocage is composed of nanoparticles.
Electrochemical performance test
Characterization of Co prepared in this example using an Iviumstat electrochemical workstation2V2O7The mass specific capacitance and the cycling stability of the hollow nano cage/graphene electrode material are improved. As shown in fig. 4 and 5, the results show that: at a current density of 1A/g, the Co2V2O7The specific capacity of the hollow nano cage/graphene is 576F/g, the capacity of the hollow nano cage/graphene is reserved at 360F/g under the current density of 20A/g, the material has excellent rate performance, the material also has excellent cycling stability, and the capacity is attenuated by 7% after the material is cycled for 10000 times.
Example 2
Step (1): preparation of ZIF-67/graphene
Ultrasonically dispersing 10mg of graphene oxide powder in 50mL of methanol, adding 2mmol of cobalt nitrate, and stirring to obtain a solution A for later use.
8mmol of 2-methylimidazole were dissolved in 50mL of methanol to obtain a solution B for further use.
And slowly adding the solution B into the solution A, stirring for 5 minutes, and standing at room temperature for 24 hours to obtain ZIF-67/graphene for later use.
Step (2): preparation of Co2V2O7Hollow nanocage/graphene composite material
Ultrasonically dispersing the ZIF-67/graphene prepared in the step (1) into 20mL of ethanol solution to obtain a solution C for later use.
1.6mmol of ammonium metavanadate is dissolved in 20ml of an ammonia water/water mixed solution to obtain a solution D for later use.
Slowly adding the solution C into the solution D, stirring, and keeping the temperature at 80 ℃ for 1h to obtain Co2V2O7Hollow nanocages/graphene.
Electrochemical performance test
Characterization of Co prepared in this example using an Iviumstat electrochemical workstation2V2O7The mass specific capacitance and the cycling stability of the hollow nano cage/graphene electrode material are improved. The results show that: at a current density of 1A/g, the Co2V2O7The specific capacity of the hollow nano cage/graphene is 412F/g, 298F/g of the capacity is reserved under the current density of 20A/g, the material also has excellent cycling stability, and the capacity is attenuated by 10% after the material is cycled for 10000 times.
Example 3
Step (1): preparation of ZIF-67/graphene
And ultrasonically dispersing 40mg of graphene oxide powder in 50mL of methanol, adding 2mmol of cobalt nitrate, and stirring to obtain a solution A for later use.
8mmol of 2-methylimidazole were dissolved in 50mL of methanol to obtain a solution B for use.
And slowly adding the solution B into the solution A, stirring for 5 minutes, and standing at room temperature for 24 hours to obtain ZIF-67/graphene for later use.
Step (2): preparation of Co2V2O7Hollow nanocage/graphene composite material
Ultrasonically dispersing the ZIF-67/graphene prepared in the step (1) into 20mL of ethanol solution to obtain a solution C for later use.
1.6mmol of ammonium metavanadate is dissolved in 20ml of an ammonia water/water mixed solution to obtain a solution D for later use.
Slowly adding the solution C into the solution D, stirring, and keeping the temperature at 80 ℃ for 1h to obtain Co2V2O7Hollow nanocages/graphene.
Electrochemical performance test
Characterization of Co prepared in this example using an Iviumstat electrochemical workstation2V2O7The mass specific capacitance and the cycling stability of the hollow nano cage/graphene electrode material are improved. The results show that: at a current density of 1A/g, the Co2V2O7The specific capacity of the hollow nano cage/graphene is 396F/g, under the current density of 20A/g, the capacity of the hollow nano cage/graphene is reserved at 246F/g, the material also has excellent cycling stability, and the capacity is attenuated by 8.4% after the material is cycled for 10000 times.
Comparative example 1
Step (1): preparation of ZIF-67
2mmol of cobalt nitrate was added to 50mL of methanol, and the mixture was stirred to obtain a solution A for use.
8mmol of 2-methylimidazole were dissolved in 50mL of methanol to obtain a solution B for use.
And slowly adding the solution B into the solution A, stirring for 5 minutes, and standing at room temperature for 24 hours to obtain ZIF-67 for later use.
Step (2): preparation of Co2V2O7Hollow nanometer cage
And (2) ultrasonically dispersing the ZIF-67 prepared in the step (1) into 20mL of ethanol solution to obtain a solution C for later use.
1.6mmol of ammonium metavanadate is dissolved in 20ml of an ammonia water/water mixed solution to obtain a solution D for later use.
Slowly adding the solution C into the solution D, stirring, and keeping the temperature at 80 ℃ for 1h to obtain Co2V2O7A hollow nanocage.
Electrochemical performance test
Characterization of Co prepared in this example using an Iviumstat electrochemical workstation2V2O7The mass specific capacitance and the cycling stability of the hollow nano cage electrode material. The results show that: at a current density of 1A/g, the Co2V2O7The specific capacity of the hollow nano cage is 337F/g, the capacity of the hollow nano cage is reserved at 186F/g under the current density of 20A/g, and the capacity is attenuated by 22.7 percent after circulation for 10000 times.
Co of the invention2V2O7The hollow nanocage/graphene can obtain the aboveExcellent electrochemical performance because:
(1) the graphene has the characteristics of high conductivity, good physical and chemical stability and the like, can enhance the conductivity of the electrode material, and can be used for Co in a cycle test2V2O7The hollow nanometer cage plays a role in buffering and protecting, and the circulation stability of the material is enhanced.
(2)Co2V2O7The hollow structure has a special hollow structure consisting of nano particles, has a larger specific surface area, provides more electrochemical active sites and is beneficial to the generation of electrochemical reaction.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or equivalents thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Although the embodiments of the present invention have been described with reference to the accompanying drawings, it is not intended to limit the scope of the present invention, and it should be understood by those skilled in the art that various modifications and variations can be made without inventive efforts by those skilled in the art based on the technical solution of the present invention.
Claims (10)
1. Co2V2O7The preparation method of the hollow nano cage/graphene composite material is characterized by comprising the following steps:
adding cobalt salt into the dispersion liquid of the graphene oxide, and uniformly mixing to obtain a solution A;
mixing the solution A with an alcoholic solution of 2-methylimidazole, and standing to form ZIF-67/graphene;
carrying out ion exchange reaction on ZIF-67/graphene and metavanadate to form Co2V2O7Hollow nanocage/graphene composite material。
2. Co according to claim 12V2O7The preparation method of the hollow nano cage/graphene composite material is characterized in that the molar ratio of the cobalt salt to the 2-methylimidazole is 1: 2-8.
3. Co according to claim 12V2O7The preparation method of the hollow nano cage/graphene composite material is characterized in that the mass ratio of graphene oxide to 2-methylimidazole is (1-3): 3 to 10.
4. Co according to claim 12V2O7The preparation method of the hollow nano cage/graphene composite material is characterized in that the mass concentration of the graphene oxide dispersion liquid is 0.2-0.6 mg/mL.
5. Co according to claim 12V2O7The preparation method of the hollow nano cage/graphene composite material is characterized in that the standing condition is as follows: standing at room temperature for 6-24 h.
6. Co according to claim 12V2O7The preparation method of the hollow nano cage/graphene composite material is characterized in that the ion exchange reaction comprises the following specific steps: mixing the ZIF-67/graphene dispersion solution with a metavanadate solution, and keeping the temperature at 60-80 ℃ for 0.5-2 h.
7. Co according to claim 62V2O7The preparation method of the hollow nanocage/graphene composite material is characterized in that the mass concentration of the ZIF-67/graphene dispersion liquid is 3-5 mg/mL.
8. Co according to claim 62V2O7The preparation method of the hollow nanocage/graphene composite material is characterized in that the metavanadate solution isDissolving metavanadate in an ammonia water/water mixed solution, wherein the volume ratio of ammonia water to water is 1-5: 15-19.
9. Co prepared by the method of any one of claims 1 to 82V2O7A hollow nanocage/graphene composite material.
10. Co of claim 92V2O7The application of the hollow nano cage/graphene composite material in preparing the super capacitor.
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| CN115083799A (en) * | 2022-06-30 | 2022-09-20 | 江苏大学 | Macroporous self-supporting CNTs @ Co 2 V 2 O 7 Preparation method and application of composite film with black phosphorus quantum dots loaded thereon |
| CN115064680B (en) * | 2022-06-29 | 2024-04-30 | 上海空间电源研究所 | Cu for thermal battery2V2O7Composite positive electrode material of nano cage-shaped conductive substrate and preparation method thereof |
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| CN115083799A (en) * | 2022-06-30 | 2022-09-20 | 江苏大学 | Macroporous self-supporting CNTs @ Co 2 V 2 O 7 Preparation method and application of composite film with black phosphorus quantum dots loaded thereon |
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