CN106935416B - A kind of starfish shape δ-MnO2Nanometer sheet/carbon fiber paper combination electrode material preparation method - Google Patents
A kind of starfish shape δ-MnO2Nanometer sheet/carbon fiber paper combination electrode material preparation method Download PDFInfo
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- CN106935416B CN106935416B CN201710013930.4A CN201710013930A CN106935416B CN 106935416 B CN106935416 B CN 106935416B CN 201710013930 A CN201710013930 A CN 201710013930A CN 106935416 B CN106935416 B CN 106935416B
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- carbon fiber
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/40—Fibres
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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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- 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
Abstract
The invention belongs to inorganic non-metallic material preparation field more particularly to a kind of starfish shape δ-MnO2Nanometer sheet/carbon fiber paper combination electrode material preparation method.It is sufficiently mixed dissolution with soluble manganese salt and soluble sulphite in aqueous solution, will clean and dried carbon fiber paper immerses above-mentioned mixed solution, by hydro-thermal reaction, obtains starfish shape δ-MnO after washing is dry2Nanometer sheet/carbon fiber paper combination electrode material.The raw material of preparation method of the present invention is cheap and easy to get, synthesis technology is simple and easy, preparation cost is low, contamination-free generates, products therefrom novel in shape, and is closely grown on the fiber stick of carbon fiber paper.Synthesized manganese dioxide, the diameter of extra large star topology is between 300~500nm, and the thickness of starfish shape nanometer sheet is between 10~30nm, and synthesized material is uniformly dispersed, pattern is uniform, can be directly used as the electrode material of supercapacitor.In 1mol/L NaSO4In electrolyte, when current density is 1A/g, the specific capacitance value of gained combination electrode material is up to 336F/g.
Description
Technical field
The invention belongs to inorganic non-metallic material preparation field more particularly to a kind of starfish shape δ-MnO2Nanometer sheet/carbon fiber
The preparation method of paper combination electrode material.
Background technique
Supercapacitor is due to its high power density, fast charge-discharge velocity, the cycle life of length and more traditional electricity
The higher energy density of container and as next-generation very important energy storage device, have been to be concerned by more and more people.Super electricity
The performance of container depends primarily on electrode material, and what report was used as electrode material for super capacitor mainly includes carbon material, metal
Oxide/hydroxide and conducting polymer materials, among a variety of materials, manganese dioxide is due to its unique physical chemistry
Matter should widely be made catalyst, magnetic material, lithium ion battery and supercapacitor.In particular, manganese dioxide is because of its valence
Lattice are cheap, raw material resources are abundant, environmental-friendly and up to 1370F/g theoretical specific volume and be considered very promising super
The electrode material of grade capacitor.
The chemical property of electrode material largely by the crystal structure of themselves, size, dimension, especially
It is the influence of appearance structure, because these factors can largely influence the electric conductivity and structural stability of electrode material
And electrolyte ion is in the diffusion rate of electrode material surface.In the manganese dioxide of different-shape, three-dimensional sheet structure
Manganese dioxide is received significant attention since it is generally configured with preferable chemical property.
But it is difficult the material that synthesis has three-dimensional appearance in the case where not adding any template or surfactant
Material.Currently, preparing the manganese dioxide of starfish shape nanometer sheet pattern using a step hydrothermal synthesis, there is not been reported.
Summary of the invention
The present invention prepares starfish shape δ-MnO by a step hydrothermal synthesis method2Nanometer sheet/carbon fiber paper combination electrode material
Material.
The present invention provides a kind of starfish shape δ-MnO2Nanometer sheet/carbon fiber paper combination electrode material preparation method, it is special
Sign is: soluble potassium permanganate and sulphite are sufficiently dissolved in aqueous solution；It will clean and dried carbon fiber
Paper, which is immersed in above-mentioned mixed solution, carries out hydro-thermal reaction, after complete reaction, up to purpose after products therefrom is washed, is dry
Product.
Above-mentioned sulphite is one or two kinds of mixtures of potassium sulfite or sodium sulfite.
The molar ratio of above-mentioned soluble potassium permanganate and soluble sulphite is 1:1.5.
Above-mentioned hydrothermal temperature is 100~160 DEG C, and the hydro-thermal reaction time is 18~36h.
Above-mentioned drying temperature is 70 DEG C, drying time 12h.
The present invention have it is following the utility model has the advantages that
(1) raw material of preparation method provided by the present invention is cheap and easy to get, resourceful, and synthesis technology is simple and easy, closes
At stable product quality and good process repeatability.
(2) present invention has prepared novel starfish shape manganese dioxide nano-plates array structure, and synthesized material
Size is more uniform, is uniformly dispersed, in the synthesis process without adding any template or surfactant.
(3) when the starfish shape manganese dioxide nano-plates prepared by the present invention do electrode of super capacitor, in 1A/g electric current
Its specific capacitance value is up to 336F/g under density.
Detailed description of the invention
Fig. 1 is that starfish shape manganese dioxide nano-plates/carbon fiber paper combination electrode material X-ray prepared by the present invention is spread out
Penetrate figure.
Fig. 2 is starfish shape manganese dioxide nano-plates/carbon fiber paper combination electrode material scanning electricity prepared by the present invention
Mirror figure.
Fig. 3 is starfish shape manganese dioxide nano-plates/carbon fiber paper combination electrode material scanning electricity prepared by the present invention
Mirror figure.
Fig. 4 is starfish shape manganese dioxide nano-plates/carbon fiber paper combination electrode material scanning electricity prepared by the present invention
Mirror figure.
Fig. 5 is starfish shape manganese dioxide nano-plates/carbon fiber paper combination electrode material scanning electricity prepared by the present invention
Mirror figure.
Fig. 6 is starfish shape manganese dioxide nano-plates/carbon fiber paper combination electrode material circulation volt prepared by the present invention
Pacify performance diagram.
Fig. 7 is starfish shape manganese dioxide nano-plates/carbon fiber paper combination electrode material constant current prepared by the present invention
Charging and discharging curve figure.
Specific embodiment
The present invention is illustrated in detail with reference to the accompanying drawings and examples.
Used reagent in following embodiments is unless otherwise specified the pure grade of analysis.
Embodiment 1
1mmol potassium permanganate, 1.5mmol potassium sulfite are dissolved in 30ml distilled water first, magnetic agitation is extremely at room temperature
It is completely dissolved；Then, which is transferred in the autoclave of 50mL polytetrafluoroethyllining lining, takes and a piece of washes in advance
Net and dried carbon fiber paper, is dipped in aforesaid reaction vessel；Finally, reaction kettle is placed in 120 DEG C of thermostatic drying chambers
Reaction is for 24 hours.To which after reaction, cooled to room temperature takes out the carbon fiber paper in reaction kettle, with deionized water and anhydrous second
Alcohol intersects supersound washing for several times, finally puts it into drying in 70 DEG C of drying boxes, obtains the two of the starfish shape nanometer chip architecture
Manganese oxide/carbon fiber combination electrode material.It is δ-MnO that products therefrom crystal form, which analyzes result by X-ray powder diffraction,2, X-ray
Diffraction patterns are as shown in Figure 1；Products therefrom pattern is by electron microscope analysis, as shown in Fig. 2, Fig. 3, Fig. 4, Fig. 5, can understand in figure and see
Observe the manganese dioxide of finely dispersed starfish shape nanometer chip architecture；The chemical property of products therefrom leads under three-electrode system
Electrochemistry heart performance evaluation is crossed, under 1A/g current density, specific capacitance value is up to 336F/g.
Embodiment 2
1mmol potassium permanganate, 1.5mmol potassium sulfite are dissolved in 30ml distilled water first, magnetic agitation is extremely at room temperature
It is completely dissolved；Then, which is transferred in the autoclave of 50mL polytetrafluoroethyllining lining, takes and a piece of washes in advance
Net and dried carbon fiber paper, is dipped in aforesaid reaction vessel；Finally, reaction kettle is placed in 140 DEG C of thermostatic drying chambers
React 18h.To which after reaction, cooled to room temperature takes out the carbon fiber paper in reaction kettle, with deionized water and anhydrous second
Alcohol intersects supersound washing for several times, finally puts it into drying in 70 DEG C of drying boxes, obtains the two of the starfish shape nanometer chip architecture
Manganese oxide/carbon fiber combination electrode material.Products therefrom knows that it is starfish shape through X-ray powder diffraction, scanning electron microscope analysis
δ-the MnO of nanometer chip architecture2, specific capacitance of the product under 1A/g current density is 310F/g.
Embodiment 3
1mmol potassium permanganate, 1.5mmol sodium sulfite are dissolved in 30ml distilled water first, magnetic agitation is extremely at room temperature
It is completely dissolved；Then, which is transferred in the autoclave of 50mL polytetrafluoroethyllining lining, takes and a piece of washes in advance
Net and dried carbon fiber paper, is dipped in aforesaid reaction vessel；Finally, reaction kettle is placed in 120 DEG C of thermostatic drying chambers
Reaction is for 24 hours.To which after reaction, cooled to room temperature takes out the carbon fiber paper in reaction kettle, with deionized water and anhydrous second
Alcohol intersects supersound washing for several times, finally puts it into drying in 70 DEG C of drying boxes, obtains the two of the starfish shape nanometer chip architecture
Manganese oxide/carbon fiber combination electrode material.Products therefrom knows that it is starfish shape through X-ray powder diffraction, scanning electron microscope analysis
δ-the MnO of nanometer chip architecture2, specific capacitance of the product under 1A/g current density is 333F/g.
Embodiment 4
1mmol potassium permanganate, 1.5mmol sodium sulfite are dissolved in 30ml distilled water first, magnetic agitation is extremely at room temperature
It is completely dissolved；Then, which is transferred in the autoclave of 50mL polytetrafluoroethyllining lining, takes and a piece of washes in advance
Net and dried carbon fiber paper, is dipped in aforesaid reaction vessel；Finally, reaction kettle is placed in 120 DEG C of thermostatic drying chambers
Reaction is for 24 hours.To which after reaction, cooled to room temperature takes out the carbon fiber paper in reaction kettle, with deionized water and anhydrous second
Alcohol intersects supersound washing for several times, finally puts it into drying in 70 DEG C of drying boxes, obtains the two of the starfish shape nanometer chip architecture
Manganese oxide/carbon fiber combination electrode material.Products therefrom knows that it is starfish shape through X-ray powder diffraction, scanning electron microscope analysis
δ-the MnO of nanometer chip architecture2, specific capacitance of the product under 1A/g current density is 305F/g.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
Limitations on the scope of the patent of the present invention therefore cannot be interpreted as, as long as being obtained using the form of same replacement or equivalent transformation
Technical solution, should all fall within the scope and spirit of the invention.
Claims (2)
1. a kind of starfish shape δ-MnO2Nanometer sheet/carbon fiber paper combination electrode material preparation method, it is characterised in that: will be solvable
Property potassium permanganate and soluble sulphite be sufficiently mixed dissolution in aqueous solution；It will clean and dried carbon fiber paper
It is immersed in above-mentioned mixed solution and carries out hydro-thermal reaction, after complete reaction, will be produced after products therefrom washing, drying up to purpose
Object；The solubility sulphite is potassium sulfite；The molar ratio of the solubility potassium permanganate and soluble sulphite is
1:1.5；The hydrothermal temperature is 100~160 DEG C, and the hydro-thermal reaction time is 18~36h.
2. a kind of preparation of starfish shape δ-MnO2 nanometer sheet/carbon fiber paper combination electrode material according to claim 1
Method, it is characterised in that: wash products therefrom, drying temperature is 70 DEG C, drying time 12h.
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| CN111986931B (en) * | 2020-07-24 | 2021-10-26 | 华南理工大学 | Manganese oxide nano-structure electrode material and preparation method and application thereof |
| CN112599764B (en) * | 2020-12-28 | 2023-03-28 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method, product and application of ternary nanowire array @ carbon fiber |
| CN112981454B (en) * | 2021-02-03 | 2022-06-28 | 山东大学 | Manganese dioxide ultra-long nanowire catalyst with oxygen vacancy as well as preparation method and application thereof |
| CN114031125B (en) * | 2021-11-05 | 2023-11-28 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of ternary nano sheet@carbon nano tube anode material, product and application thereof |
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