CN112919549B - Pure phase spinel Co3O4Multistage nano-sheet, soft template preparation method thereof and application of multistage nano-sheet in super capacitor - Google Patents
Pure phase spinel Co3O4Multistage nano-sheet, soft template preparation method thereof and application of multistage nano-sheet in super capacitor Download PDFInfo
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- 239000002135 nanosheet Substances 0.000 title claims abstract description 53
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 26
- 239000011029 spinel Substances 0.000 title claims abstract description 26
- 239000003990 capacitor Substances 0.000 title abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 239000002057 nanoflower Substances 0.000 claims abstract description 19
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000010405 anode material Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 150000001868 cobalt Chemical class 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000006183 anode active material Substances 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 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
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-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
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 18
- 239000004810 polytetrafluoroethylene Substances 0.000 abstract description 13
- 229920001343 polytetrafluoroethylene Polymers 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 12
- 239000006260 foam Substances 0.000 abstract description 10
- 229910052759 nickel Inorganic materials 0.000 abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000004146 energy storage Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000000137 annealing Methods 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 239000007772 electrode material Substances 0.000 abstract description 2
- 239000002064 nanoplatelet Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- -1 Polytetrafluoroethylene Polymers 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 231100000584 environmental toxicity Toxicity 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
Classifications
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- 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
- H01G11/24—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
-
- 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
-
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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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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Abstract
The invention discloses a pure-phase spinel Co 3O4 multi-stage nano sheet, a soft template preparation method thereof and application thereof in a super capacitor, and belongs to the fields of nano energy storage structure material preparation technology and electrochemical application. According to the invention, common living sodium dodecyl sulfate is adopted as a soft template, the nano flower precursor with uniform morphology is obtained by heating in an oil bath, co 3O4 with a multi-stage nano sheet structure is obtained after proper annealing, the mixture is loaded on foam nickel after being mixed with PTFE, and the super capacitor anode with good performance can be obtained, and the specific capacitance value of the super capacitor obtained by using the anode is 342.8C.g ‑1 (the current density is 1 A.g ‑1) and 58.8% rate performance (the current density is increased by 16 times), so that the production cost is reduced, and the super capacitor has good industrial application prospect. In addition, the pure-phase spinel Co 3O4 multistage nanosheets are used for manufacturing the electrode material of the supercapacitor, carbon powder is not required to be added, manufacturing cost is simplified, contribution of carbon to a capacitor is eliminated, and performance results of the supercapacitor are more reliable.
Description
Technical Field
The invention belongs to the field of nano energy storage structure material preparation technology and electrochemical application, and particularly relates to a two-dimensional nano-sheet spinel transition metal oxide, a preparation method thereof and application thereof in a super capacitor, and more particularly relates to a pure-phase spinel Co 3O4 multi-stage nano-sheet, a soft template preparation method thereof and application thereof in the super capacitor.
Background
In the prior art, the preparation process of the spinel Co 3O4 with the two-dimensional nano-sheet structure is complex, the synthesis period is long, and the etchant has certain environmental toxicity and is not beneficial to the green development of the surrounding environment; the prepared spinel Co 3O4 is low in multiplying power performance as a supercapacitor material, and needs to be combined with other carbon materials to realize high-performance energy storage. However, the preparation of specific carbon materials (graphene and carbon nanotubes) requires more severe conditions, so that more toxic reagents are needed in the process of preparing the materials, the energy consumption is high, and the production cost is increased. In addition, the currently synthesized Co 3O4 nanoflower needs a high-pressure environment of a reaction kettle, so that the operation danger is increased intangibly; or the foam metal substrate is used for growing the nano material with uniform size, and the growth amount is small, so that the large-scale production and application cannot be realized, and the subsequent practical industrialized development is not facilitated.
Sodium Dodecyl Sulfate (SDS) is a common surfactant in life, and has been widely used in many fields such as batteries, supercapacitors, and the like as a structure-oriented soft template. The nature and structure of the two-dimensional nanomaterial play a key role in the energy storage property of the supercapacitor. Due to the low energy density of supercapacitors, the selection of suitable materials and methods to increase their energy density has become a critical issue. Therefore, the super capacitor material with high rate performance and the preparation method thereof are developed, and the super capacitor material has important significance for improving the energy density of the super capacitor.
The present application has been made for the above reasons.
Disclosure of Invention
Aiming at the problems or defects existing in the prior art, the invention aims to provide a pure-phase spinel Co 3O4 multi-stage nano sheet, a soft template preparation method thereof and application thereof in super capacitors.
In order to achieve one of the above objects of the present invention, the present invention adopts the following technical scheme:
A preparation method of a pure-phase spinel Co 3O4 multi-stage nano-sheet soft template specifically comprises the following steps:
(1) Mixing soluble cobalt salt, urea and Sodium Dodecyl Sulfate (SDS), adding deionized water, uniformly mixing, transferring the obtained mixture into an oil bath, heating to 120 ℃ and refluxing and stirring for reaction for 4 hours, obtaining a light blue solution after the reaction is finished, filtering, washing and drying the obtained light blue solution while the solution is hot to obtain a blue solid, namely a Co 3O4 multistage nanosheet precursor;
(2) Transferring the blue solid obtained in the step (1) into a crucible, then placing the crucible filled with the blue solid into a furnace chamber of a resistance furnace, heating to 400 ℃, calcining for 2 hours at a constant temperature, and cooling to room temperature after the reaction is finished to obtain black solid, namely the pure-phase spinel Co 3O4 multi-stage nano-sheet.
Further, in the above technical solution, in the step (1), the soluble cobalt salt may be any one of cobalt chloride, cobalt sulfate, cobalt nitrate, cobalt chloride hexahydrate, cobalt sulfate heptahydrate, and cobalt nitrate hexahydrate, and more preferably cobalt chloride hexahydrate.
Further, according to the technical scheme, in the step (1), the addition ratio of the soluble cobalt salt, urea and sodium dodecyl sulfate is 2.4mmol:8.4mmol:12mmol.
Further, in the above technical solution, the dosage ratio of the soluble cobalt salt to deionized water in the step (1) is preferably 2.4mmol:240mL.
Further, according to the technical scheme, the urea in the step (1) plays a role in the invention: urea is used as a precipitator, and is alkalescent in water, so that soluble cobalt salt is gradually hydrolyzed to generate cobalt hydroxide in alkalescent environment.
Further, according to the above technical solution, the Sodium Dodecyl Sulfate (SDS) in step (1) plays a role in the present invention: as a morphology control agent, cobalt hydroxide is promoted to grow directionally, and a nanometer flower-shaped structure with uniform morphology is formed. If sodium dodecyl sulfate is not added in the invention, a large amount of precipitate is formed after the reaction in the step (1), which is unfavorable for forming a specific nanoflower morphology, and the energy storage property of the prepared target product (pure-phase spinel Co 3O4 multi-stage nanosheets) is also drastically reduced.
Further, according to the technical scheme, in the step (1), deionized water and absolute ethyl alcohol are adopted for washing for several times. More preferably, deionized water is used for washing for 2 times, and absolute ethyl alcohol is used for washing for 1 time.
Further, according to the technical scheme, the specific drying process in the step (1) is as follows: drying at constant temperature in an oven at 60 ℃ for 24 hours.
Further, according to the technical scheme, in the step (1), the blue solid is a Co 3O4 multistage nano-sheet precursor, and is in a nano-flower structure formed by sheet assembly, the diameter of the nano-flower is about 500-600nm, the thickness of the flower sheet is 20-40nm, and the diameter of the flower hole is 200-250nm.
Further, in the above technical solution, in the step (2), the resistance furnace is preferably a ceramic fiber resistance furnace.
Further, in the above technical scheme, the heating rate of the resistance furnace in the step (2) is not limited, and may be, for example, 1 to 40 ℃/min, and more preferably 1 to 10 ℃/min.
Further, in the above technical scheme, in step (2), after the Co 3O4 multi-stage nanosheet precursor is calcined, the diameter of the nanoflower of the Co 3O4 multi-stage nanosheet precursor is not greatly changed, but the thickness of the flower is increased, and the flower is adhered and aggregated to form a Co 3O4 multi-stage nanosheet structure, wherein: the diameter of the nanometer flower is about 500-600nm, and the thickness of the flower piece is 30-50nm.
The second object of the invention is to provide pure-phase spinel Co 3O4 multi-stage nano-sheets prepared by the method.
The third object of the invention is to provide the application of the pure-phase spinel Co 3O4 multi-stage nano-sheet prepared by the method as an anode active material in a super capacitor.
The anode material of the supercapacitor consists of an anode active material and an adhesive, wherein the anode active material is the pure-phase spinel Co 3O4 multistage nano-sheet prepared by the soft template method.
Further, in the above-described aspect, the adhesive is any one of Polytetrafluoroethylene (PTFE), polyvinylidene fluoride, cellulose, styrene-butadiene rubber, and the like, and more preferably polytetrafluoroethylene.
Further, according to the technical scheme, the mass ratio of the pure-phase spinel Co 3O4 multi-stage nano-sheet of the anode active material to the adhesive can be 10-25:1, more preferably 19:1.
The anode of the supercapacitor comprises a current collector and an anode material coated and/or filled on the current collector, wherein the anode material is the anode material of the supercapacitor.
Further, according to the technical scheme, the current collector is any one of foam nickel, copper sheet or foam copper.
The utility model provides a supercapacitor, includes positive pole, negative pole, sets up diaphragm, electrolyte and the casing between positive and negative pole, wherein: the anode is the anode of the super capacitor.
The core innovation points of the invention are as follows:
Co 3O4 of the invention is a multi-stage nano-sheet structure in the form of nanoflower. According to the invention, sodium dodecyl sulfate is adopted as a soft template, the nano flower precursor with uniform morphology is obtained by heating in an oil bath, co 3O4 with a multi-stage nano sheet structure is obtained after proper annealing, and the Co 3O4 is mixed with PTFE and then loaded on a current collector, so that the super capacitor anode with good performance can be obtained, the anode is simple to prepare, does not contain conductive agents (such as carbon powder and the like), the influence of electric double layer capacitance of the carbon powder can be eliminated, and each index evaluation of the super capacitor performance is more objective and more real.
Compared with the prior art, the preparation method of the pure-phase spinel Co 3O4 multi-stage nano-sheet and the soft template thereof and the application in the super capacitor have the following beneficial effects:
(1) The pure-phase spinel Co 3O4 multistage nano-sheet is obtained by heating SDS as a soft template oil bath and calcining, and is used as an anode active material of the super capacitor, and the specific capacitance value of the obtained super capacitor is 342.8C.g -1 (the current density is 1 A.g -1) and 58.8% rate capability (the current density is increased by 16 times), so that the production cost is reduced, and the super capacitor has good industrial application prospect.
(2) The electrode material of the super capacitor is manufactured by using the pure-phase spinel Co 3O4 multi-stage nano-sheet without adding carbon powder, so that the manufacturing cost is simplified, the contribution of carbon to the capacitor is eliminated, and the performance result of the super capacitor is more reliable.
(3) The Sodium Dodecyl Sulfate (SDS) adopted by the invention is a common surfactant for living, and has the advantages of low price, no toxicity, low cost and no harm to the environment.
(4) The preparation method has the advantages of simple process, mild reaction, easily available raw materials, low price and no pollution to the environment, can realize large-scale production and application, and is favorable for subsequent actual industrialized development.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of a Co 3O4 multi-stage nanoplatelet precursor prepared according to example 1 of the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) image of Co 3O4 multi-stage nanoplatelets prepared in example 1 of the present invention;
FIG. 3 is an XRD pattern of a Co 3O4 multi-stage nanoplatelet prepared in example 1 of the present invention; wherein: the abscissa is 2 times the diffraction angle and the ordinate is the diffraction intensity;
FIG. 4 is a plot of the constant current timing voltage for the Co 3O4 multi-stage nanoplatelets prepared in example 1 of the present invention; wherein: the abscissa is discharge time and the ordinate is potential;
FIG. 5 is a graph showing the variation of specific capacitance with current density and the rate performance of Co 3O4 multi-stage nanoplatelets prepared in example 1 of the present invention; wherein: the abscissa is current density, the left ordinate is specific capacitance, and the right ordinate is rate capability.
Detailed Description
The invention is described in further detail below by way of examples. The present embodiment is implemented on the premise of the present technology, and a detailed embodiment and a specific operation procedure are now given to illustrate the inventive aspects of the present invention, but the scope of protection of the present invention is not limited to the following embodiments.
Various modifications to the precise description of the application will be readily apparent to those skilled in the art from the information contained herein without departing from the spirit or scope of the appended claims. It is to be understood that the scope of the application is not limited to the defined processes, properties or components, as these embodiments, as well as other descriptions, are merely illustrative of specific aspects of the application. Indeed, various modifications of the embodiments of the application which are obvious to those skilled in the art or related fields are intended to be within the scope of the following claims.
For a better understanding of the present application, and not to limit its scope, all numbers expressing quantities, percentages, and other values used in the present application are to be understood as being modified in all instances by the term "about". Each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
The test methods used in the following examples are conventional methods unless otherwise specified; the raw materials, reagents and the like used, unless otherwise specified, are those commercially available from conventional commercial sources and the like.
Example 1
The preparation method of the pure-phase spinel Co 3O4 multi-stage nano-sheet soft template in the embodiment specifically comprises the following steps:
(1) Preparation of Co 3O4 multistage nanosheet precursor
0.5710G of cobalt chloride hexahydrate (CoCl 2·6H2 O), 0.5043g of urea and 3.4606g of Sodium Dodecyl Sulfate (SDS) are sequentially added into a 500mL single-neck flask, 240mL of deionized water is poured into the flask, the flask is placed into an oil bath pot, the temperature is controlled at 120 ℃, reflux stirring and heating are carried out for 4 hours, the solution is changed from pink to light blue, after the reaction is completed, the solution is filtered while the solution is hot, the solution is filtered by vacuum filtration through a filter membrane with the thickness of 0.22 mu m, then the solution is washed clean by hot water and hot ethanol, a blue wafer-shaped solid is obtained, and the wafer-shaped solid is dried for 24 hours at the temperature of 60 ℃ in an oven, thus obtaining the nanoflower formed by sheet assembly.
(2) Preparation of Co 3O4 multi-stage nanosheets
And (3) loading the Co 3O4 precursor nanoflower obtained in the step (1) into a crucible, placing the crucible into a ceramic fiber resistance furnace, calcining at 400 ℃ for 2 hours to obtain black solid, and grinding the black solid into powder to obtain the Co 3O4 multistage nanosheets.
FIG. 1 is a Scanning Electron Microscope (SEM) picture of a Co 3O4 multi-stage nanoplatelet precursor prepared in example 1 of the present invention, from which it can be seen that the nanoflower is assembled in nanoplatelets, the diameter of the nanoflower is about 500-600nm, the thickness of the flower flake is 20-40nm, and the diameter of the flower hole is 200-250nm.
FIG. 2 is a Scanning Electron Microscope (SEM) picture of a Co 3O4 multi-stage nanosheet prepared in example 1 of the present invention, which shows that the obtained sample is in the form of a multi-stage nanosheet, the nanoflower is still visible, the diameter of the nanoflower is about 500-600nm, and the thickness of the flower sheet is increased by 30-50nm.
Fig. 3 is an XRD pattern of the multi-stage nano-sheet of Co 3O4 prepared in example 1 of the present invention, from which it can be seen that the obtained sample is well matched with the standard card, indicating that the sample is spinel Co 3O4.
The electrical property test method comprises the following steps:
(a) Modification of foam nickel
The mass ratio of Co 3O4 multi-stage nano-sheet prepared in example 1 to Polytetrafluoroethylene (PTFE) is 95:5, mixing: the 60wt% PTFE concentrate was diluted with absolute ethanol to a PTFE solution having a concentration of 7.08 mg/mL -1, then 74.3. Mu.L of the PTFE solution having a concentration of 7.08 mg/mL -1 was measured, 10mg of the Co 3O4 multi-stage nanosheets prepared in example 1 were added, and the mixture was uniformly dispersed by ultrasound. Then drop-wise adding the obtained product onto the known foam nickel (the foam nickel is treated by ultrasonic treatment with 2M HCl, deionized water and absolute ethyl alcohol in turn for 30min in advance to remove nickel oxide and oil stains on the surface, then drying at 80 ℃ for 24h, weighing for standby), baking by an infrared lamp, and compacting by a glass sheet. Drying at 80 ℃ for 24 hours, weighing the foam nickel again, wherein the quality of the foam nickel is poor twice, namely the quality of the loaded Co 3O4 multi-stage nano-sheet and PTFE. The total mass of the loaded Co 3O4 multi-stage nano-sheet and PTFE is calculated to be 0.9mg, the mass of the actual Co 3O4 multi-stage nano-sheet is calculated to be 0.855mg, and the mass of PTFE is calculated to be 0.045mg.
(B) Electrochemical testing
Taking the modified foam nickel in the step (a) as a working electrode, a platinum sheet as a counter electrode and a Saturated Calomel Electrode (SCE) as a reference electrode, firstly performing a 100 mV.s -1 Cyclic Voltammetry (CV) test in a 2M KOH solution, scanning for 10 circles until the nickel is stable, then scanning for two circles of CV under 50 mV.s -1, and taking the CV of the second circle to evaluate the CV behavior of Co 3O4; and then, respectively testing the charge-discharge curves of the Co 3O4 multi-stage nano-sheet by using a fixed current density of 1 A.g -1,2A·g-1,4A·g-1,8A·g-1,16A·g-1 by a timing voltage method to obtain the specific capacitance and the rate performance index of the material.
FIG. 4 is a plot of the constant current timing voltage of the Co 3O4 multi-stage nanoplatelets in step (b) above. From this figure, it can be seen that the current density was 1a·g -1 to 16a·g -1 and the discharge time was sequentially reduced from 342.8s to 12.6s.
FIG. 5 is a graph showing the specific capacitance versus current density and the rate performance of the Co 3O4 multi-stage nanoplatelets in step (b). From this graph, it can be seen that when the current density is 1a·g -1, the specific capacitance is 342.8c·g -1, and when the current density is increased 16 times, the specific capacitance is 201.6c·g -1, which is 58.8% of the initial value, and higher specific capacitance and rate capability are exhibited.
The super capacitor obtained by utilizing the Co 3O4 multi-stage nano-sheet has the excellent electrochemical performance, and the Co 3O4 is of a multi-stage nano-sheet structure with nano flowers, the appearance of the nano flowers increases the specific surface area of the material, increases the contact area of the material and electrolyte, and is beneficial to the penetration and permeation of ions on the surface of the material, so that the super capacitor has higher specific capacitance, and in addition, the uniform and thin nano-sheet is beneficial to the rapid removal of ions from the surface of the material, so that the super capacitor has higher multiplying power performance.
In conclusion, the specific capacitance value of the Co 3O4 multi-stage nano-sheet prepared by the soft template method is 342.8C.g -1 (the current density is 1 A.g -1) and 58.8% rate performance (the current density is increased by 16 times), and the Co 3O4 multi-stage nano-sheet can be applied to super capacitors under alkaline conditions.
Claims (4)
1. An anode material of a supercapacitor, which consists of an anode active material and a binder, and is characterized in that: the anode active material is a pure-phase spinel Co 3O4 multi-stage nano sheet, and the pure-phase spinel Co 3O4 multi-stage nano sheet is prepared by adopting the following method, and comprises the following steps:
(1) Mixing soluble cobalt salt, urea and sodium dodecyl sulfate, adding deionized water, uniformly mixing, transferring the obtained mixture into an oil bath, heating to 120 ℃ and refluxing at constant temperature, stirring for reaction for 4 hours, obtaining a bluish solution after the reaction is finished, filtering, washing and drying the obtained bluish solution while the bluish solution is hot to obtain a bluish solid, namely a Co 3O4 multistage nanosheet precursor; the addition ratio of the soluble cobalt salt, urea and sodium dodecyl sulfate is 2.4mmol:8.4mmol:12mmol; the Co 3O4 multi-stage nanosheet precursor is in a sheet-shaped assembled nanoflower structure, the diameter of the nanoflower is 500-600nm, the thickness of the flower sheet is 20-40nm, and the diameter of the flower hole is 200-250nm;
(2) Transferring the blue solid obtained in the step (1) into a crucible, then placing the crucible filled with the blue solid into a furnace chamber of a resistance furnace, heating to 400 ℃, calcining for 2 hours at a constant temperature, and cooling to room temperature after the reaction is finished to obtain black solid, namely the pure-phase spinel Co 3O4 multi-stage nano-sheet; the diameter of the nanoflower in the Co 3O4 multi-stage nano sheet is 500-600nm, and the thickness of the flower sheet is 30-50nm.
2. The supercapacitor anode material according to claim 1, wherein: the soluble cobalt salt in the step (1) is any one of cobalt chloride, cobalt sulfate, cobalt nitrate, cobalt chloride hexahydrate, cobalt sulfate heptahydrate and cobalt nitrate hexahydrate.
3. An anode of a supercapacitor, the anode comprising a current collector and an anode material coated and/or filled on the current collector, characterized in that: the anode material is the supercapacitor anode material of claim 1.
4. The utility model provides a supercapacitor, includes positive pole, negative pole, sets up diaphragm, electrolyte and the casing between positive and negative pole, its characterized in that: the anode is the supercapacitor anode of claim 3.
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| CN108287186A (en) * | 2017-01-09 | 2018-07-17 | 天津大学 | A kind of device of detection lead ion |
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