CN110002501A - A kind of manganese dioxide electrode material for super capacitor and preparation method and application - Google Patents
A kind of manganese dioxide electrode material for super capacitor and preparation method and application Download PDFInfo
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- CN110002501A CN110002501A CN201910289104.1A CN201910289104A CN110002501A CN 110002501 A CN110002501 A CN 110002501A CN 201910289104 A CN201910289104 A CN 201910289104A CN 110002501 A CN110002501 A CN 110002501A
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 239000003990 capacitor Substances 0.000 title claims abstract description 55
- 239000007772 electrode material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 38
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 25
- 239000008103 glucose Substances 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000013019 agitation Methods 0.000 claims abstract description 8
- 230000005291 magnetic effect Effects 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000006230 acetylene black Substances 0.000 claims description 5
- 239000004744 fabric Substances 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 238000007710 freezing Methods 0.000 claims description 3
- 230000008014 freezing Effects 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 230000006641 stabilisation Effects 0.000 claims 1
- 238000011105 stabilization Methods 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 239000010405 anode material Substances 0.000 abstract 1
- 229960000935 dehydrated alcohol Drugs 0.000 abstract 1
- 230000007547 defect Effects 0.000 description 26
- 125000004430 oxygen atom Chemical group O* 0.000 description 26
- UBXWAYGQRZFPGU-UHFFFAOYSA-N manganese(2+) oxygen(2-) titanium(4+) Chemical compound [O--].[O--].[Ti+4].[Mn++] UBXWAYGQRZFPGU-UHFFFAOYSA-N 0.000 description 16
- 239000003792 electrolyte Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 238000004435 EPR spectroscopy Methods 0.000 description 3
- 229910013868 M2SO4 Inorganic materials 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 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
- 239000007788 liquid Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000001075 voltammogram Methods 0.000 description 2
- 229920002307 Dextran Polymers 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 239000006181 electrochemical material Substances 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000005406 washing 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
- C01G45/00—Compounds of manganese
- C01G45/02—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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- 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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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2006/40—Electric properties
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/42—Magnetic 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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- Microelectronics & Electronic Packaging (AREA)
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Abstract
The invention discloses a kind of manganese dioxide electrode material for super capacitor and preparation method and application, preparation method has the characteristics that cost is relatively low, simple process, energy conservation and environmental protection.Potassium permanganate is dissolved in deionized water and forms solution, glucose solution is added dropwise in liquor potassic permanganate again under the conditions of certain temperature water-bath and magnetic agitation, continue stirring 5 hours, filtered and washed with deionized water and dehydrated alcohol, finally carries out being freeze-dried up to the electrode material.Its material structure presents three-dimensional netted and with a large amount of mesoporous, has biggish specific surface area.Be used as super capacitor anode material, under specific capacitance with higher i.e. 2 A/g current densities, specific capacitance up to specific capacitance conservation rate after 340.8 F/g and good cyclical stability i.e. 3000 time circulation constant current charge-discharge be 98%.
Description
Technical field
The invention belongs to field of nanometer material technology and electrochemical material fields, are related to a kind of manganese dioxide electrode of super capacitor
Material and preparation method and application more particularly to a kind of nano material of manganese dioxide and system with oxygen atom vacancy defect structure
Preparation Method further relates to application of the nano material of manganese dioxide as electrode material in manufacture supercapacitor.
Background technique
Electric energy (hydroelectric generation), solar energy, wind energy belong to the green regenerative energy sources of sustainable development, can alleviate
The depletion rate as caused by today's society rapid economic development be continuously increased and non-renewable petroleum resources crisis and
Atmosphere pollution, carbon dioxide excess emissions lead to environmental crisis caused by weather change dramatically.Although solar energy, wind energy are certainly
It is distributed more widely but limited by natural cause and be unable to duration and carry out energy conversion and storage in right boundary, therefore there is an urgent need to open
Send out have can the electrochemical energy storage device of dependence meet the rigid need in people's production and living.Electrochemical energy storage device includes two
Primary cell, supercapacitor and fuel cell, wherein supercapacitor is a kind of very important energy-storage travelling wave tube.Supercapacitor
Also known as electric chemical super capacitor is the energy storage device between traditional capacitor and battery.The highest function of supercapacitor
Rate density is far longer than the maximum power density of all kinds of secondary rechargeable batteries, and fast charging and discharging may be implemented；And supercapacitor
Highest energy density be also far longer than the highest energy density of conventional dielectric capacitor, show that it can store more electricity
Lotus.Have both that charge/discharge speed is fast, has extended cycle life, the advantages that coulombic efficiency is high, operational safety, life of the supercapacitor in people
Generating in living has very extensive purposes, including portable electronic device, hybrid vehicle and wireless telecommunications etc. wide
Big field.
According to charge storage mechanisms, there are two different modes with conversion process for the energy storage of supercapacitor: one
Planting is electric double layer formula principle, condenser type (fake capacitance) principle subject to another kind, while supercapacitor is divided into two classes again, i.e., double
Electric layer capacitor and pseudocapacitors.The specific capacitance of double layer capacitor is often smaller, energy density is lower；On the contrary, pseudocapacitors
More charges can be stored on the electrode by the mechanism of its redox reaction, solve capacitor energy density and ask
Topic.In numerous fake capacitance electrode materials, for manganese dioxide with its rich reserves, environment compatibility is preferable, and market economy is lower, work
Make the advantages such as higher, the theoretical specific capacitance high (1237 F/g) of voltage to receive significant attention.However the internal resistance of manganese dioxide is larger, shadow
Ring the performance of manganese bioxide electrochemical performance.The method for improving manganese dioxide electric conductivity at present has manganese dioxide and other high electricity
Conductance carbon material (including graphene, redox graphene, carbon nanotube etc.) or metal oxide are compound, to improve electrode
The whole conductivity of material.Although this method can improve the electric conductivity of manganese dioxide electrode but since there are manganese dioxide and lead
Electric material interface cannot still improve the electric conductivity of manganese dioxide essence, and the complex process of synthesising complex, at high cost, unfavorable
In expanding production.
Summary of the invention
The purpose of the present invention is for the poor problem of manganese dioxide electric conductivity, provide a kind of simple process, reaction time
It is short, cost is relatively low, the preferable manganese dioxide electrode material for super capacitor of electric conductivity and preparation method.
The present invention more free-revving engine is to improve manganese dioxide conductivity problems using oxygen atom vacancy defect structure, and
Application as electrode of super capacitor.
Realizing the object of the invention specific technical solution is:
A kind of preparation method of manganese dioxide electrode material for super capacitor, this method are that potassium permanganate and glucose difference is molten
In deionized water, and glucose solution is placed in water bath and carries out magnetic agitation；Liquor potassic permanganate is added dropwise
In glucose solution, stirring 5 hours is then proceeded to；To cooled to room temperature after reaction, obtained solid substance spend from
Sub- water and washes of absolute alcohol are for several times, last freeze-dried to get the manganese dioxide electrode material for super capacitor；Its
In: the ratio between mole of potassium permanganate and glucose is 1:1 ~ 3；The temperature of water-bath is 30 ~ 60 DEG C；Freeze-drying is using dry in freezing
It is 12 ~ 24 hours dry under the conditions of -50 DEG C constantly vacuumized in dry machine.
Manganese dioxide electrode material for super capacitor made from a kind of method described above.
A kind of material described above is preparing the application on electrode of super capacitor.
The application, feature are: by the manganese dioxide electrode material for super capacitor and acetylene black, Kynoar
(PVDF) it is scattered in after mixing in polyvinylpyrrolidone (NMP), stirs 30 minutes and form stable suspension；It will hang again
Supernatant liquid is coated on hydrophilic carbon cloth, and 60 DEG C are dried in vacuo 12 hours；Obtain electrode of super capacitor；Wherein, manganese dioxide is super
Capacitor electrode material and the mass ratio of acetylene black, Kynoar (PVDF) are 75:20:5；Polyvinylpyrrolidone (NMP)
Mass ratio with manganese dioxide electrode material for super capacitor is 8:1；Quality coated in the mixed liquor on hydrophilic carbon cloth is 2 ~ 3
mg/cm2。
Beneficial effects of the present invention
Preparation method of the invention has the characteristics that cost of material is lower, operating procedure is simple, energy conservation and environmental protection, is easier to realize
Industrial volume production.On the one hand prepared manganese dioxide electrode material for super capacitor has loose and porous structure feature, favorably
In in the supercapacitor course of work electrolyte permeability to material internal；On the other hand the manganese dioxide super capacitor of its preparation
Device electrode material has oxygen atom void geometry defect characteristic, can effectively improve the electric conductivity of manganese dioxide.By prepared two
Manganese oxide electrode material for super capacitor and active carbon are assembled into Asymmetric Supercapacitor, have biggish energy density, energy
It is enough effectively to solve the problems, such as that conventional Super capacitor energy density is lower.
Detailed description of the invention
Fig. 1 is the X diffraction spectrogram (XRD) of manganese dioxide electrode material for super capacitor of the invention；
Fig. 2 is the electron paramagnetic resonance figure (EPR) of manganese dioxide electrode material for super capacitor of the invention；
Fig. 3 is the Flied emission electron-microscope scanning figure (FESEM) of manganese dioxide electrode material for super capacitor of the invention；
Fig. 4 is the adsorption isothermal curve and pore size distribution curve figure of manganese dioxide electrode material for super capacitor of the invention
(BET)；
Fig. 5 is the linear voltammogram (LSV) of manganese dioxide electrode material for super capacitor of the invention；
Fig. 6 is manganese dioxide electrode of super capacitor of the invention in 1 M Li2SO4Following under different scanning rates in electrolyte
Ring volt-ampere curve figure；
Fig. 7 is manganese dioxide electrode of super capacitor of the invention in 1 M Li2SO4Perseverance in electrolyte under different current densities
Flow charging and discharging curve figure；
Fig. 8 is manganese dioxide electrode of super capacitor of the invention in 1 M Li2SO4In electrolyte, under 3 A/g current densities
Constant current charge-discharge stable circulation figure；
Fig. 9 is that manganese dioxide electrode of super capacitor of the invention is anode, the simulation super capacitor that active carbon is cathode assembling
The energy density figure of device.
Specific embodiment
Preparation and its electrode below by specific embodiment to manganese dioxide electrode material for super capacitor of the invention
The preparation of material and chemical property are further described.
1, the preparation of manganese dioxide electrode material for super capacitor
Manganese dioxide electrode material for super capacitor of the invention is the nano-manganese dioxide with oxygen atom vacancy defect structure
Preparation method: material using potassium permanganate as starting material, using dextran particles as reducing agent, passes through liquid under water bath condition
The nano material of manganese dioxide precursor with oxygen atom vacancy defect structure is made in phase reaction；Precursor is dry through filtration washing, freezing
It is dry, obtain final products.Its specific preparation process are as follows: potassium permanganate and glucose powder are dissolved in deionized water respectively, and
Glucose solution is placed in 30 ~ 60 DEG C of water baths and carries out magnetic agitation.Glucose is added dropwise in liquor potassic permanganate again
In solution, stirring 5 hours is then proceeded to.To cooled to room temperature after reaction, obtained solid substance deionized water and
Several times, most afterwards -50 DEG C of warp are freeze-dried 12 ~ 24 hours to get manganese dioxide electrode of super capacitor material to washes of absolute alcohol
Material.
The ratio between mole of the potassium permanganate and glucose is 1:1 ~ 1:3.
2, the structural characterization of the nanometer titanium dioxide manganese material with oxygen atom vacancy defect structure
Below by X-ray diffraction (XRD), field emission scanning electron microscope (FESEM), specific surface area measuring instrument (BET), linear volt-ampere
(LSV) structure of the nanometer titanium dioxide manganese material prepared by the present invention with oxygen atom vacancy defect structure is carried out specifically
It is bright.
Fig. 1 is the X-ray spectrogram of the nanometer titanium dioxide manganese material prepared by the present invention with oxygen atom vacancy defect structure
(XRD).As can be seen from Figure 1 the peak of the standard diagram (JCPDS 18-0802) of all diffraction maximum positions and manganese dioxide
Position is consistent.Wherein blue shift occurs compared with standard card for (002) diffraction maximum, and illustrating manganese dioxide crystals, there are oxygen atom skies
Position defect sturcture.And other impurities diffraction maximum is not present in XRD diffraction spectrogram, illustrate that the material purity of preparation is very high.
Fig. 2 is that the electron paramagnetic of the nanometer titanium dioxide manganese material prepared by the present invention with oxygen atom vacancy defect structure is total
Vibration figure (EPR).It can be seen from the figure that there is a pair of of vibration peak at g value 2.002, further illustrate that the material of preparation has
Oxygen atom vacancy defect feature.
Fig. 3 is that the Flied emission of the nanometer titanium dioxide manganese material prepared by the present invention with oxygen atom vacancy defect structure scans
Electron microscope (SEM).As can be seen from the figure nanometer sheet is stacked to form three-dimensional netted hole structure.
Fig. 4 is that the isothermal adsorption of the nanometer titanium dioxide manganese material prepared by the present invention with oxygen atom vacancy defect structure is bent
Line and pore size distribution curve (BET).IV type is presented in adsorption isothermal curve, and showing material, there are meso pore characteristics.By graph of pore diameter distribution
It is found that manganese dioxide prepared by the present invention is to have maximum pore capacities at 14.0 nm in aperture, sample average aperture is 20.2 nm,
Specific surface area is 202.65 m2/g.Test result shows that obtained manganese dioxide has good pore structure and biggish ratio
Surface area, these excellent surface textures and internal gutter structure come into full contact with electrolyte and electrode material, are conducive to
The abundant progress of electrochemical reaction.
Fig. 5 is the linear voltammogram of the nanometer titanium dioxide manganese material prepared by the present invention with oxygen atom vacancy defect structure
(LSV).It can be seen from the figure that under identical voltage conditions, the prepared manganese dioxide electricity with oxygen atom vacancy defect
It is larger to flow the common manganese dioxide of response ratio, illustrates that internal resistance is smaller.
3, chemical property
Below by electrochemical workstation CHI660E to the nano-silica prepared by the present invention with oxygen atom vacancy defect structure
The chemical property for changing manganese material is described in detail.
A) preparation of electrode of super capacitor
By the nanometer titanium dioxide manganese material produced by the present invention with oxygen atom vacancy defect structure and acetylene black, PVDF according to
Totally 6.00 mg are scattered in 5 mL nmp solvents the hybrid solid powder that the mass ratio of 75:20:5 is formed, shape after stirring 30 minutes
At uniform suspension, hydrophilic carbon cloth is dipped in suspension, the drying 12 hours of 60 DEG C of vacuum is to get test electrode.
B) electrochemical property test
Fig. 6 is the nanometer titanium dioxide manganese material prepared by the present invention with oxygen atom vacancy defect structure as super capacitor electrode
Li of the pole in 1 M2SO4The different cyclic voltammetry curves (CV) swept under speed in electrolyte, operating voltage window are (0-1.2) V.Knot
Fruit shows there are a pair of of redox peaks on the CV curve of sample, and the feature of Faraday pseudo-capacitance is presented.With sweep speed
Increase, the shape of CV curve is held essentially constant, and illustrates that the capacitor multiplying power of material is preferable, is had and is done the latent of electrode of super capacitor
Energy.
Fig. 7 is the nanometer titanium dioxide manganese material prepared by the present invention with oxygen atom vacancy defect structure as super capacitor
Li of the device electrode in 1 M2SO4In electrolyte, operating voltage window is (0-1.2) V, the constant current charge and discharge under different current densities
Electric curve graph.It will be appreciated from fig. 6 that symmetrical structure is presented in charging and discharging curve, its reversible redox property is embodied.Work as current density
When for 2 A/g, the specific capacitance of electrode can achieve 340.8 F/g；When current density is 10 A/g, the specific capacitance of electrode still may be used
It is maintained at 229.2 F/g.Illustrate that material of the invention has good capacitance behavior, this and cyclic voltammetry result phase one
It causes.
Fig. 8 is the nanometer titanium dioxide manganese material prepared by the present invention with oxygen atom vacancy defect structure as super capacitor
Li of the device electrode in 1 M2SO4In electrolyte, operating voltage window is (0-1.2) V, and when current density is 10 A/g, circulation is steady
Fixed figure.As seen from the figure, after 3000 cycle charge-discharges, under the capacity retention of manganese dioxide electrode does not occur significantly
Drop, remains at 98%, illustrates that manganese dioxide produced by the present invention has good cyclical stability.
Fig. 9 is the nanometer titanium dioxide manganese material prepared by the present invention with oxygen atom vacancy defect structure as super capacitor
Device anode, the analog capacitor energy density figure that active carbon is cathode assembling.It can be seen from the figure that being in power density
When 8148.64 w/kg, energy density reaches 98.01 wh/kg；When power density is 59428.27 w/kg, energy density is still
It can reach 31.53 wh/kg, illustrate that the manganese dioxide prepared by the present invention with oxygen atom vacancy defect has good electrification
Learn performance.
Embodiment 1
(1) 2.37 g glucose and 1.26 g potassium permanganate are weighed in container, are separately added into 80 mL and 50mL deionized waters,
It stirs to dissolve；
(2) glucose solution is put into 60 DEG C of water-baths and carries out magnetic agitation, Portugal then is added dropwise in liquor potassic permanganate
In grape sugar juice, after being added dropwise, continues stirring 5 hours, react it sufficiently.
(3) obtained solid matter deionized water and ethyl alcohol are cleaned repeatedly, finally -50 DEG C in freeze drier
It is 12 hours dry, obtain the nanometer titanium dioxide manganese material with oxygen atom vacancy defect structure.Through detecting, the material is in 2 A/
Specific capacitance under g current density reaches 340.8 F/g.
Embodiment 2
(1) 2.37 g glucose and 1.26 g potassium permanganate are weighed in container, are separately added into 80 mL and 50mL deionized waters,
It stirs to dissolve；
(2) glucose solution is put into 30 DEG C of water-baths and carries out magnetic agitation, Portugal then is added dropwise in liquor potassic permanganate
In grape sugar juice, after being added dropwise, continues stirring 5 hours, react it sufficiently.
(3) obtained solid matter deionized water and ethyl alcohol are cleaned repeatedly, finally -50 DEG C in freeze drier
It is 12 hours dry, obtain the nanometer titanium dioxide manganese material with oxygen atom vacancy defect structure.Through detecting, the material is in 2 A/
Specific capacitance under g current density reaches 304 F/g.
Embodiment 3
(1) 1.44 g glucose and 1.26 g potassium permanganate are weighed in container, are separately added into 80 mL and 50mL deionized waters,
It stirs to dissolve；
(2) glucose solution is put into 60 DEG C of water-baths and carries out magnetic agitation, Portugal then is added dropwise in liquor potassic permanganate
In grape sugar juice, after being added dropwise, continues stirring 5 hours, react it sufficiently.
(3) obtained solid matter deionized water and ethyl alcohol are cleaned repeatedly, finally -50 DEG C in freeze drier
It is 12 hours dry, obtain the nanometer titanium dioxide manganese material with oxygen atom vacancy defect structure.Through detecting, the material is in 2 A/
Specific capacitance under g current density reaches 244 F/g.
Embodiment 4
(1) 5.04 g glucose and 1.26 g potassium permanganate are weighed in container, are separately added into 80 mL and 50mL deionized waters,
It stirs to dissolve；
(2) glucose solution is put into 60 DEG C of water-baths and carries out magnetic agitation, Portugal then is added dropwise in liquor potassic permanganate
In grape sugar juice, after being added dropwise, continues stirring 5 hours, react it sufficiently.
(3) obtained solid matter deionized water and ethyl alcohol are cleaned repeatedly, finally -50 DEG C in freeze drier
It is 12 hours dry, obtain the nanometer titanium dioxide manganese material with oxygen atom vacancy defect structure.Through detecting, the material is in 2 A/
Specific capacitance under g current density reaches 384 F/g.
Claims (4)
1. a kind of preparation method of manganese dioxide electrode material for super capacitor, which is characterized in that this method is by potassium permanganate
It is dissolved in deionized water respectively with glucose, and glucose solution is placed in water bath and carries out magnetic agitation；By permanganic acid
Potassium solution is added dropwise in glucose solution, then proceedes to stirring 5 hours；To cooled to room temperature after reaction, gained
Solid matter deionized water and washes of absolute alcohol are for several times, last freeze-dried to get the manganese dioxide super capacitor
Device electrode material；Wherein: the ratio between mole of potassium permanganate and glucose is 1:1 ~ 3；The temperature of water-bath is 30 ~ 60 DEG C；Freezing is dry
It is dry using 12 ~ 24 hours dry under the conditions ofs constantly vacuumized in freeze drier -50 DEG C.
2. manganese dioxide electrode material for super capacitor made from a kind of claim 1 the method.
3. material described in a kind of claim 2 is preparing the application on electrode of super capacitor.
4. application according to claim 3, which is characterized in that by the manganese dioxide electrode material for super capacitor and second
Acetylene black, Kynoar (PVDF) are scattered in after mixing in polyvinylpyrrolidone (NMP), stir the stabilization of formation in 30 minutes
Suspension；Suspension is coated on hydrophilic carbon cloth again, 60 DEG C are dried in vacuo 12 hours；Obtain electrode of super capacitor；Its
In, the mass ratio of manganese dioxide electrode material for super capacitor and acetylene black, Kynoar is 75:20:5；Polyvinyl pyrrole
The mass ratio of alkanone and manganese dioxide electrode material for super capacitor is 8:1；Quality coated in the mixed liquor on hydrophilic carbon cloth
For 2 ~ 3 mg/cm2。
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| CN102107909A (en) * | 2011-01-11 | 2011-06-29 | 中国科学院上海硅酸盐研究所 | Method for preparing mesoporous nano manganese dioxide |
| CN108421545A (en) * | 2018-03-08 | 2018-08-21 | 清华大学 | Manganese dioxide composite material and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102107909A (en) * | 2011-01-11 | 2011-06-29 | 中国科学院上海硅酸盐研究所 | Method for preparing mesoporous nano manganese dioxide |
| CN108421545A (en) * | 2018-03-08 | 2018-08-21 | 清华大学 | Manganese dioxide composite material and its preparation method and application |
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| CN113921804A (en) * | 2021-10-11 | 2022-01-11 | 燕山大学 | Electrochemical preparation method of monatomic manganese catalyst |
| CN113921804B (en) * | 2021-10-11 | 2022-12-27 | 燕山大学 | Electrochemical preparation method of monatomic manganese catalyst |
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