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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- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 239000004005 microsphere Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- 239000007772 electrode material Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 15
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 239000003990 capacitor Substances 0.000 claims abstract description 9
- 150000001868 cobalt Chemical class 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 239000002135 nanosheet Substances 0.000 claims abstract description 6
- 230000014759 maintenance of location Effects 0.000 claims abstract description 5
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims abstract description 3
- 238000000137 annealing Methods 0.000 claims abstract description 3
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims abstract description 3
- 239000002243 precursor Substances 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 25
- 239000002002 slurry Substances 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 18
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 16
- 239000007795 chemical reaction product Substances 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 239000011230 binding agent Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000006258 conductive agent Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 239000002033 PVDF binder Substances 0.000 claims description 9
- 239000006230 acetylene black Substances 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 229940011182 cobalt acetate Drugs 0.000 claims description 9
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- -1 polytetrafluoroethylene Polymers 0.000 claims description 9
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- 239000011889 copper foil Substances 0.000 claims description 2
- 239000006260 foam Substances 0.000 claims description 2
- 239000011888 foil Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 230000005476 size effect Effects 0.000 abstract description 3
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 238000002309 gasification Methods 0.000 abstract description 2
- 238000000197 pyrolysis Methods 0.000 abstract description 2
- 238000001338 self-assembly Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 14
- 238000005303 weighing Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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, LIGHT-SENSITIVE OR TEMPERATURE-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
- 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
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
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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