CN108962617B - Preparation method and application of self-assembled cobaltosic oxide hierarchical microsphere - Google Patents
Preparation method and application of self-assembled cobaltosic oxide hierarchical microsphere 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
- H01G11/22—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
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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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- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a preparation method and application of self-assembled cobaltosic oxide graded microspheres, wherein the preparation method comprises the following steps: dispersing cobalt salt and polyvinyl alcohol in a mixed solution of ethylene glycol and deionized water, obtaining a cobalt hydroxide precursor by using a hydrothermal method, and performing high-temperature annealing treatment to finally obtain cobaltosic oxide microspheres with a hierarchical structure formed by self-assembly of two-dimensional nanosheets; the cobaltosic oxide hierarchical microsphere is particularly applied to a super capacitor electrode material, and the specific capacitance retention rate is over 70 percent. According to the invention, by utilizing the pyrolysis gasification property of polyvinyl alcohol, a large number of hollow micropores are generated in the cobaltosic oxide structure, the porosity and the specific surface area of the cobaltosic oxide structure are improved, the active sites are increased, and the prepared cobaltosic oxide microspheres have the micro-nano size effect and the grading characteristic, so that the agglomeration problem caused by undersize is effectively avoided, and the electrochemical performance of the cobaltosic oxide microspheres is improved.
Description
Technical Field
The invention belongs to the technical field of electrode materials of super capacitors, and particularly relates to a preparation method and application of self-assembled cobaltosic oxide hierarchical microspheres.
Background
The super capacitor is also called as an electrochemical capacitor, is a secondary energy storage device capable of directly storing charges, has higher power density, longer cycle, shorter charging time and higher energy efficiency compared with the traditional electrostatic capacitor and secondary battery, and has wide application prospect in the aspects of mobile electronic industry, new energy storage systems, pure electric vehicles and the like.
What plays decisive role in the super capacitor is electrode material, according to the difference of electrode material theory of operation, can divide into two main categories: one is an electric double layer electrode material represented by a carbon-based material, and the other is a pseudocapacitance electrode material based on a transition metal compound or a conductive polymer. The pseudocapacitance material not only comprises electric double layer charge storage, but also comprises charges stored by redox reaction of electrolyte ions on the surface of the material, so that the capacity can be improved by one to two orders of magnitude, the specific capacity and the energy density are greatly improved, and the pseudocapacitance material becomes a focus of attention of researchers. The pseudocapacitance materials studied at present mainly comprise: ruthenium dioxide, manganese oxide, vanadium oxide, nickel oxide, cobaltosic oxide and the like, wherein cobaltosic oxide is considered to be one of materials with high research potential due to the advantages of low price, abundant natural resources, excellent electron storage capacity, extremely high theoretical non-capacitance (up to 3500F/g) and the like.
In recent years, cobaltosic oxide with various microstructures and special shapes has been successfully prepared, for example, chinese patent CN103011306B authorizes a method for preparing nano-scale cubic cobaltosic oxide, chinese patent CN104787806B authorizes a rosette-shaped nano-cobaltosic oxide and a preparation method thereof, chinese patent CN103247777B authorizes a cobaltosic oxide multi-shell hollow sphere cathode material for lithium ion batteries and a preparation method thereof, and chinese patent CN103979616B authorizes a preparation method of rosette-shaped cobaltosic oxide, and the like. At present, no report related to self-assembly of cobaltosic oxide nanosheets into hierarchical microspheres is found.
Disclosure of Invention
The invention aims to prepare cobaltosic oxide with micro-nano size effect and hierarchical structure; the invention also aims to provide application of the material as a supercapacitor electrode material, and a supercapacitor electrode made of the material has good electrochemical performance, high specific capacitance and stable cycle characteristics. In order to realize the purpose, the invention provides a preparation method and application of self-assembled cobaltosic oxide hierarchical microspheres.
The technical scheme of the invention is summarized as follows:
a preparation method of self-assembled cobaltosic oxide hierarchical microspheres comprises the steps of dispersing cobalt salt and polyvinyl alcohol in a mixed solution of ethylene glycol and deionized water, obtaining a cobalt hydroxide precursor by a hydrothermal method, and finally obtaining cobaltosic oxide microspheres with hierarchical structures formed by self-assembling two-dimensional nanosheets through high-temperature annealing treatment, wherein the preparation method specifically comprises the following steps:
(1) mixing ethylene glycol and deionized water according to the volume ratio of 5:1-1:5, adding 1-4mmol of divalent inorganic cobalt salt into 15-50mL of mixed solution, adding 0.01-0.5g of polyvinyl alcohol, and stirring at room temperature for 0.5-1 h;
(2) transferring the mixed solution to a polytetrafluoroethylene lining reaction kettle, and carrying out hydrothermal reaction for 6-24h at the temperature of 150-;
(3) naturally cooling the reaction product to room temperature, centrifuging and washing, drying the obtained precipitate for 12h at 60 ℃, heating to 600 ℃ at the heating rate of 1-10 ℃/min, and calcining at constant temperature for 2-4h to obtain the self-assembled cobaltosic oxide graded microsphere.
Preferably, the divalent inorganic cobalt salt is one of cobalt acetate, cobalt nitrate, cobalt sulfate and cobalt chloride.
Preferably, the washing operation process comprises the following steps: the separated precipitate is washed 5-8 times with deionized water.
The invention also provides an application of the self-assembled cobaltosic oxide hierarchical microsphere, the self-assembled cobaltosic oxide hierarchical microsphere is specifically applied to a super capacitor electrode material, and the specific capacitance retention rate of the electrode material is up to more than 70%.
Preferably, the preparation process of the supercapacitor electrode material is as follows:
(1) mixing cobaltosic oxide, a conductive agent and a binder according to the mass ratio of (7-8) to (1-2) to 1, adding the mixture into N-methyl pyrrolidone, and performing ultrasonic dispersion to obtain slurry;
(2) uniformly coating the slurry on a substrate, drying in vacuum at 80-120 ℃ for 12-24h, and tabletting under the pressure of 10-20 MPa.
Preferably, the conductive agent is one of acetylene black, graphite and Super P.
Preferably, the binder is one of PVDF and PTFE.
Preferably, the substrate is one of nickel foam, copper foil, aluminum foil and carbon paper. The invention has the beneficial effects that:
(1) the invention takes the polyvinyl alcohol as the structure directing agent for synthesizing the cobaltosic oxide for the first time, utilizes the pyrolysis gasification property of the polyvinyl alcohol to generate a large amount of cobaltosic oxide hierarchical structures with hollow interiors, and the design of hollow pore channels improves the porosity and the specific surface area of the cobaltosic oxide, increases active sites and ensures that the cobaltosic oxide has excellent electrochemical characteristics;
(2) the method adopts a one-step hydrothermal method, does not add any template agent or surfactant, and has the advantages of simple experimental operation, mild reaction conditions and good repeatability;
(3) the invention self-assembles the microsphere with a hierarchical structure through the formed nano sheets under the hydrothermal condition;
(4) the cobaltosic oxide microspheres prepared by the method have a micro-nano size effect, and meanwhile, the formed hierarchical structure can effectively avoid the problem of agglomeration caused by undersize, so that the cobaltosic oxide microspheres are beneficial to application in the field of energy storage;
(5) the supercapacitor electrode made of the material has good electrochemical performance, high specific capacitance and stable cycle characteristics.
Drawings
FIG. 1 is an X-ray diffraction pattern (XRD) of the product obtained in example 1;
FIG. 2 is a Scanning Electron Micrograph (SEM) of the product obtained in example 1;
FIG. 3 is a cyclic voltammogram of the product prepared in example 1 as an electrode material of a supercapacitor at a sweep rate of 10mV/s in 6mol/L KOH electrolyte;
FIG. 4 is a plot of constant current discharge of the supercapacitor electrode material of example 1 in a 6mol/LKOH electrolyte at different current densities;
FIG. 5 is a graph of specific capacitance of cobaltosic oxide graded microspheres prepared in example 1 at different current densities.
Detailed Description
The present invention is further described in detail below with reference to specific embodiments and the attached drawings so that those skilled in the art can practice the invention with reference to the description.
Example 1
Weighing 0.5g of cobalt acetate and 0.02g of PVA, dissolving in 15ml of deionized water, stirring for 30min, weighing 15ml of ethylene glycol, adding the ethylene glycol into the solution, stirring for 30min, transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining, heating for 24h at the temperature of 180 ℃ in an oven, naturally cooling to room temperature, centrifugally separating a reaction product, washing for 5 times by using the deionized water, drying for 12h at the temperature of 60 ℃, and calcining the reaction product for 2h in a 400 ℃ tubular furnace to obtain the finally required cobaltosic oxide product.
Mixing the obtained cobaltosic oxide with acetylene black serving as a conductive agent and PVDF serving as a binder according to the mass ratio of 8:1:1, uniformly dispersing the mixture in N-methylpyrrolidone (NMP) to form slurry, uniformly coating the slurry on a foamed nickel substrate, drying the foamed nickel substrate for 24 hours at the temperature of 80 ℃ in a drying oven, and then performing tabletting treatment under the pressure of 10 MPa.
Example 2
Weighing 0.5g of cobalt acetate and 0.05g of PVA, dissolving in 15ml of deionized water, stirring for 30min, weighing 15ml of ethylene glycol, adding the ethylene glycol into the solution, stirring for 30min, transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining, heating for 24h at the temperature of 180 ℃ in an oven, naturally cooling to room temperature, centrifugally separating a reaction product, washing for 6 times by using the deionized water, drying for 12h at the temperature of 60 ℃, and calcining the reaction product for 2h in a 400 ℃ tubular furnace to obtain the finally required cobaltosic oxide product.
Mixing the obtained cobaltosic oxide with acetylene black serving as a conductive agent and PVDF serving as a binder according to the mass ratio of 8:1:1, uniformly dispersing the mixture in N-methylpyrrolidone (NMP) to form slurry, uniformly coating the slurry on a foamed nickel substrate, drying the foamed nickel substrate for 24 hours at the temperature of 80 ℃ in a drying oven, and then performing tabletting treatment under the pressure of 10 MPa.
Example 3
Weighing 0.5g of cobalt acetate and 0.02g of PVA, dissolving in 25ml of deionized water, stirring for 30min, weighing 5ml of ethylene glycol, adding into the solution, stirring for 30min, transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining, heating for 24h at the temperature of 180 ℃ in an oven, naturally cooling to room temperature, centrifugally separating a reaction product, washing for 6 times by using the deionized water, drying for 12h at the temperature of 60 ℃, and calcining the reaction product for 2h in a 400 ℃ tubular furnace to obtain the finally required cobaltosic oxide product.
Mixing the obtained cobaltosic oxide with acetylene black serving as a conductive agent and PVDF serving as a binder according to the mass ratio of 8:1:1, uniformly dispersing the mixture in N-methylpyrrolidone (NMP) to form slurry, uniformly coating the slurry on a foamed nickel substrate, drying the foamed nickel substrate for 24 hours at the temperature of 80 ℃ in a drying oven, and then performing tabletting treatment under the pressure of 10 MPa.
Example 4
Weighing 0.5g of cobalt acetate and 0.02g of PVA, dissolving in 15ml of deionized water, stirring for 30min, weighing 15ml of ethylene glycol, adding into the solution, stirring for 30min, transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining, heating for 24h at the temperature of an oven of 150 ℃, naturally cooling to room temperature, centrifugally separating a reaction product, washing for 7 times by using the deionized water, drying for 12h at the temperature of 60 ℃, and calcining the reaction product for 2h in a 400 ℃ tubular furnace to obtain the finally required cobaltosic oxide product.
Mixing the obtained cobaltosic oxide with acetylene black serving as a conductive agent and PVDF serving as a binder according to the mass ratio of 8:1:1, uniformly dispersing the mixture in N-methylpyrrolidone (NMP) to form slurry, uniformly coating the slurry on a foamed nickel substrate, drying the foamed nickel substrate for 24 hours at the temperature of 80 ℃ in a drying oven, and then performing tabletting treatment under the pressure of 10 MPa.
Example 5
Weighing 0.5g of cobalt acetate and 0.02g of PVA, dissolving in 15ml of deionized water, stirring for 30min, weighing 15ml of ethylene glycol, adding the ethylene glycol into the solution, stirring for 30min, transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining, heating for 12h at the temperature of an oven of 180 ℃, naturally cooling to room temperature, centrifugally separating a reaction product, washing for 7 times by using the deionized water, drying for 12h at the temperature of 60 ℃, and calcining the reaction product for 2h in a 400 ℃ tubular furnace to obtain the finally required cobaltosic oxide product.
Mixing the obtained cobaltosic oxide with acetylene black serving as a conductive agent and PVDF serving as a binder according to the mass ratio of 8:1:1, uniformly dispersing the mixture in N-methylpyrrolidone (NMP) to form slurry, uniformly coating the slurry on a foamed nickel substrate, drying the foamed nickel substrate for 24 hours at the temperature of 80 ℃ in a drying oven, and then performing tabletting treatment under the pressure of 10 MPa.
Example 6
Weighing 0.5g of cobalt acetate and 0.02g of PVA, dissolving in 15ml of deionized water, stirring for 30min, weighing 15ml of ethylene glycol, adding the ethylene glycol into the solution, stirring for 30min, transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining, heating for 24h at the temperature of an oven of 180 ℃, naturally cooling to room temperature, centrifugally separating a reaction product, washing for 8 times by using the deionized water, drying for 12h at the temperature of 60 ℃, and calcining the reaction product for 2h in a 600 ℃ tubular furnace to obtain the finally required cobaltosic oxide product.
Mixing the obtained cobaltosic oxide with acetylene black serving as a conductive agent and PVDF serving as a binder according to the mass ratio of 8:1:1, uniformly dispersing the mixture in N-methylpyrrolidone (NMP) to form slurry, uniformly coating the slurry on a foamed nickel substrate, drying the foamed nickel substrate for 24 hours at the temperature of 80 ℃ in a drying oven, and then performing tabletting treatment under the pressure of 10 MPa.
Example 7
Weighing 0.5g of cobalt acetate and 0.02g of PVA, dissolving in 15ml of deionized water, stirring for 30min, weighing 15ml of ethylene glycol, adding the ethylene glycol into the solution, stirring for 30min, transferring the mixed solution into a reaction kettle with a polytetrafluoroethylene lining, heating for 24h at the temperature of an oven of 180 ℃, naturally cooling to room temperature, centrifugally separating a reaction product, washing for 8 times by using the deionized water, drying for 12h at the temperature of 60 ℃, and calcining the reaction product for 4h in a 400 ℃ tubular furnace to obtain the finally required cobaltosic oxide product.
Mixing the obtained cobaltosic oxide with acetylene black serving as a conductive agent and PVDF serving as a binder according to the mass ratio of 8:1:1, uniformly dispersing the mixture in N-methylpyrrolidone (NMP) to form slurry, uniformly coating the slurry on a foamed nickel substrate, drying the foamed nickel substrate for 24 hours at the temperature of 80 ℃ in a drying oven, and then performing tabletting treatment under the pressure of 10 MPa.
Characterization and electrochemical performance tests were performed on the self-assembled cobaltosic oxide graded microspheres prepared in example 1 to confirm the beneficial effects of the present invention.
FIG. 1 is an XRD spectrum of the product prepared in example 1, and the diffraction peaks in the spectrum are completely consistent with those of standard Tab JCPDS 42-1467 and are typical characteristic diffraction peaks of cobaltosic oxide with a spinel structure, and no other impurity characteristic peaks appear.
FIG. 2 is an SEM image of the product obtained in example 1, which shows that the microspheres with a hierarchical structure are formed by regularly assembling nano sheets, and the interior of the microspheres penetrate through hollow pores, and the particle size is 5-20 μm.
FIG. 3 is a cyclic voltammetry graph of the product prepared in example 1 as an electrode material of a supercapacitor at a sweep rate of 10mV/s in 6mol/L KOH electrolyte, and it can be seen that the peak current of the reduction peak in the graph reaches 20mA and the peak current of the oxidation peak is-15 mA, that is, the cobaltosic oxide product as the electrode material has an obvious redox process and is a typical pseudocapacitance reaction mechanism.
FIG. 4 is a graph of the constant current discharge curve of the electrode material of the supercapacitor described in example 1 in 6mol/L KOH electrolyte with a potential window ranging from 0 to 0.54V at different current densities. As can be seen from the figure, when the current density is 1A/g, the specific capacitance of the electrode reaches 265.9F/g, which indicates that the material has the potential of being used as a super capacitor.
FIG. 5 is a graph of specific capacitance of cobaltosic oxide graded microspheres prepared in example 1 at different current densities. As can be seen from the figure, when the current densities are respectively 1A/g, 2A/g, 3A/g, 4A/g, 5A/g, 7A/g and 10A/g, the specific capacitances are respectively 265.9F/g, 259.2F/g, 251.1F/g, 244.4F/g, 235F/g, 223.3F/g and 207F/g, and when the current density is increased from 1A/g to 10A/g, the specific capacitance retention rate of the electrode material of the supercapacitor prepared by the invention is up to 78%.
While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of application of the invention, and further modifications may readily be effected by those skilled in the art, so that the invention is not limited to the specific details without departing from the general concept defined by the claims and the scope of equivalents.
Claims (8)
1. A preparation method of self-assembled cobaltosic oxide hierarchical microspheres is characterized by comprising the following steps: dispersing cobalt salt and polyvinyl alcohol in a mixed solution of ethylene glycol and deionized water, obtaining a cobalt hydroxide precursor by using a hydrothermal method, and finally obtaining cobaltosic oxide microspheres with a hierarchical structure formed by self-assembling two-dimensional nanosheets through high-temperature annealing treatment, wherein the preparation method specifically comprises the following steps:
(1) mixing ethylene glycol and deionized water according to the volume ratio of 5:1-1:5, adding 1-4mmol of divalent inorganic cobalt salt into 15-50mL of mixed solution, adding 0.01-0.5g of polyvinyl alcohol, and stirring at room temperature for 0.5-1 h;
(2) transferring the mixed solution to a polytetrafluoroethylene lining reaction kettle, and carrying out hydrothermal reaction for 6-24h at the temperature of 150-;
(3) naturally cooling the reaction product to room temperature, centrifuging and washing, drying the obtained precipitate for 12h at 60 ℃, heating to 600 ℃ at the heating rate of 1-10 ℃/min, and calcining at constant temperature for 2-4h to prepare the self-assembled cobaltosic oxide graded microspheres;
the self-assembled cobaltosic oxide hierarchical microsphere is particularly applied to an electrode material of a super capacitor, and the specific capacitance retention rate of the electrode material is up to more than 70%.
2. The method for preparing self-assembled cobaltosic oxide hierarchical microspheres according to claim 1, wherein the divalent inorganic cobalt salt is one of cobalt acetate, cobalt nitrate, cobalt sulfate and cobalt chloride.
3. The method for preparing self-assembled cobaltosic oxide hierarchical microspheres according to claim 1, wherein the washing operation comprises the following steps: the separated precipitate is washed 5-8 times with deionized water.
4. The use of the self-assembled cobaltosic oxide microspheres as claimed in any one of claims 1 to 3, wherein the self-assembled cobaltosic oxide microspheres are particularly used in supercapacitor electrode materials, and the specific capacitance retention of the electrode materials is up to 70% or more.
5. The application of the self-assembled cobaltosic oxide hierarchical microsphere as claimed in claim 4, wherein the supercapacitor electrode material is prepared by the following steps:
(1) mixing cobaltosic oxide, a conductive agent and a binder according to the mass ratio of (7-8) to (1-2) to 1, adding the mixture into N-methyl pyrrolidone, and performing ultrasonic dispersion to obtain slurry;
(2) uniformly coating the slurry on a substrate, drying in vacuum at 80-120 ℃ for 12-24h, and tabletting under the pressure of 10-20 MPa.
6. The use of self-assembled cobaltosic oxide microspheres according to claim 5, wherein the conductive agent is one of acetylene black, graphite and Super P.
7. The use of self-assembled cobaltosic oxide microspheres according to claim 5, wherein the binder is one of PVDF and PTFE.
8. The use of self-assembled cobaltosic oxide microspheres according to claim 5, wherein the substrate is one of nickel foam, copper foil, aluminum foil and carbon paper.
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