CN106601496A - Synthetic method for rice flower type spherical combined manganese dioxide super capacitor electrode material - Google Patents
Synthetic method for rice flower type spherical combined manganese dioxide super capacitor electrode material Download PDFInfo
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- electrode material
- manganese dioxide
- synthetic method
- soluble starch
- hybrid supercapacitor
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000007772 electrode material Substances 0.000 title claims abstract description 44
- 238000010189 synthetic method Methods 0.000 title claims abstract description 9
- 239000003990 capacitor Substances 0.000 title abstract description 9
- 241000574138 Ozothamnus diosmifolius Species 0.000 title abstract 3
- 229920002472 Starch Polymers 0.000 claims abstract description 31
- 239000008107 starch Substances 0.000 claims abstract description 31
- 235000019698 starch Nutrition 0.000 claims abstract description 31
- 239000004094 surface-active agent Substances 0.000 claims abstract description 15
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000007800 oxidant agent Substances 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 241000209094 Oryza Species 0.000 claims description 14
- 235000007164 Oryza sativa Nutrition 0.000 claims description 14
- 235000009566 rice Nutrition 0.000 claims description 14
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 10
- 239000012286 potassium permanganate Substances 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 241000894007 species Species 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- 241000790917 Dioxys <bee> Species 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 6
- 238000003760 magnetic stirring Methods 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000001473 noxious effect Effects 0.000 abstract 2
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 239000012153 distilled water Substances 0.000 abstract 1
- 238000009827 uniform distribution Methods 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 13
- 239000000243 solution Substances 0.000 description 10
- 238000002484 cyclic voltammetry Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- 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 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000004966 Carbon aerogel Substances 0.000 description 1
- LKDRXBCSQODPBY-VRPWFDPXSA-N D-fructopyranose Chemical compound OCC1(O)OC[C@@H](O)[C@@H](O)[C@@H]1O LKDRXBCSQODPBY-VRPWFDPXSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 229910018663 Mn O Inorganic materials 0.000 description 1
- 229910003176 Mn-O Inorganic materials 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 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
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—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
- H01G11/32—Carbon-based
- H01G11/44—Raw materials therefor, e.g. resins or coal
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a synthetic method for a rice flower type spherical combined manganese dioxide super capacitor electrode material. According to the method, soluble starch is dissolved in secondary distilled water, an oxidizing agent and a surfactant are added, and complete reaction is realized through magnetic stirring; manganous nitrate solution is added, stirring continues till the solution turns from transparent to light brown and finally to deep brown suspending liquid, and the rice flower type spherical combined manganese dioxide super capacitor electrode material is acquired. The method is advantaged in that unified morphology, uniform distribution and loose structure are realized, a superficial area is smaller, the material has excellent supercapacitor performance, good cyclic stability and relatively high rate capability and specific capacitance value and is a composite electrode material with excellent performance, the material has wide application prospects in hybrid vehicle and portable electron equipment fields, moreover, the method is advantaged in that raw materials are cheap and easy to get, cost is low, a preparation process is simple, no noxious material participates in reaction, no noxious material is generated, and the green environmental protection effect is realized.
Description
Technical field
The present invention relates to a kind of synthesis of manganese dioxide hybrid supercapacitor electrode material, more particularly to a species popped rice
The synthetic method of spherical manganese dioxide hybrid supercapacitor electrode material, belongs to composite and supercapacitor technologies neck
Domain.
Background technology
With the development of global economy, traditional energy（Coal, oil）It is depleted, and these Fossil fuels are insufficient
Using causing a large amount of harmful gass to discharge, huge threat is caused to the health of global environment and the mankind.Therefore, solar energy,
The new forms of energy such as wind energy, tide energy, nuclear energy, geothermal energy（Regenerative resource）By everybody extensive concern.Meanwhile, energy storage device changes
Enter and utilize also extremely urgent.Ultracapacitor is a kind of energy storage device between accumulator and traditional capacitor, both as
Accumulator is the same, there is high energy density, also remains traditional capacitor high power density this advantage, and this causes super capacitor
Device enjoys great popularity in fields such as hybrid vehicle, portable electric appts and reserve batteries.
Ultracapacitor can be divided into two classes according to the difference of energy storage principle：One class is double layer capacitor, and a class is counterfeit
Capacitor.The former adopts a series of material with carbon elements for capacitance material, such as Graphene, carbon aerogels, CNT, has been characterized in good
Electric conductivity well and cyclical stability, compared with pseudocapacitors, specific capacitance value is low.The latter adopts transition metal oxide/hydrogen
Oxide/sulfide and conducting polymer are active electrode material, are characterized in high specific capacitance value, but a disadvantage is that,
Poorly conductive, stability is also poor.
It is well known that RuO2The research beginning of metal oxide electrode material is opened, it is high with its wide electrochemical window
Theoretical specific capacitance value and it is famous, but shortcoming is also than more prominent, toxic, expensive and rare.Substitute good candidate is found
During person, MnO2People's eyes is engraved on, theoretical electric capacity reaches 1233Fg-1, low cost is environmentally friendly, but a difficult problem is also while deposit
Theoretical value is far below in, experiment value, poorly conductive, electron transfer rate is low.
The content of the invention
The purpose of the present invention is for MnO2Specific capacitance experiment value is low, poorly conductive, the problems such as cyclical stability is not good, carries
Excellent, the good cycling stability for a kind of electric conductivity, the MnO of life-span length2Combination electrode material --- the spherical titanium dioxide of class popped rice
Manganese hybrid supercapacitor electrode material；
It is a further object of the present invention to provide the preparation side of such popped rice spherical manganese dioxide hybrid supercapacitor electrode material
Method.
First, the preparation of manganese dioxide hybrid supercapacitor electrode material
The method of present invention synthesis class popped rice spherical manganese dioxide hybrid supercapacitor electrode material, is that soluble starch is molten
Solution adds oxidant and surfactant in redistilled water, it is fully reacted under magnetic agitation；Add manganese nitrate molten
Liquid continues to stir, until solution went from clear is changed into light brown and eventually forms dark-brown suspension, obtains final product the spherical dioxy of class popped rice
Change manganese hybrid supercapacitor electrode material, be designated as MnO2/C。
The oxidant is potassium permanganate, and oxidant is 1.58 with the mass ratio of soluble starch:1~4.74:1.
Surfactant is cetyl trimethylammonium bromide, and surfactant is with the mass ratio of soluble starch
0.083:1~0.25:1。
The concentration of manganese nitrate solution is 0.1M, and manganese nitrate is 1.19 with the mass ratio of soluble starch:1~3.58:1.
90 ~ the 120r/min of speed of magnetic agitation.
2nd, the pattern of manganese dioxide hybrid supercapacitor electrode material
The structure of composite is characterized below by infrared spectrum, X-ray diffraction, scanning electron microscope, with electrochemical workstation to it
Performance is analyzed explanation.
1st, infrared test
With infrared spectrometer (KBr tablettings) in 4000-400 cm–1Characterize the infrared appearance situation of composite（See Fig. 1）.Jing
Infrared spectrum shows occur MnO in figure2The characteristic peak of middle Mn-O keys, illustrates that the material for synthesizing is MnO2Nano material.
2nd, XRD tests
With Rigaku D/max-2400 type X-ray powder diffraction instrument（Radiation source be CuK α, 40 kV, 150 mA, λ=
0.15406 nm）Sample structure is tested（See Fig. 2）.X-ray powder diffraction appearance is compared with standard card, in sample
There is MnO2Nanocrystal is present.
3rd, sem test
The pattern of prepared composite matter is characterized with scanning electron microscope (SEM) photograph（See Fig. 3）Understand, nano material is in uniform nanosphere
Shape, loose, rough surface, and surface has been covered with nano-particle, pattern is spherical similar to popped rice, and specific surface area is larger, is conducive to
The raising of chemical property.Meanwhile, through elementary analysiss, learn that material surface contains a small amount of C.
3rd, the electrochemical property test of manganese dioxide hybrid supercapacitor electrode material
Hereinafter all of chemical property detection is carried out on CHI 660E electrochemical workstations, from saturated calomel electrode
For reference electrode, platinum electrode is, to electrode, to scribble active substance, scan area for 1 × 1 cm2Nickel foam be working electrode,
Electrolyte solution is 1M Na2SO4Solution.
1st, impact of the soluble starch of different amounts to specific capacitance
Potassium permanganate is taken for 3mmol（0.4740g）, the amount of Surfactant CTAB is 25 mg, and the amount of manganese nitrate is 0.358g
When, when soluble starch amount is respectively 0g, 0.1g, 0.2g, 0.3g, the cyclic voltammetry curve of the composite for obtaining is shown in Fig. 4.By
Fig. 4 understands that when without starch, the cyclic voltammetry curve of composite is asymmetrical in shape, and area is minimum；With starch
The increase of addition, area under the curve increase, when starch consumption is 0.2g, corresponding area is maximum, and shape is class rectangle,
Symmetry also preferably, illustrates the capacitance behavior that the material for synthesizing has had；When starch consumption continues to increase, 0.3g is reached, on the contrary face
Product can reduce.Illustrate that soluble starch is 1 with the mass ratio of potassium permanganate:When 2.37, the specific capacitance of composite is maximum.
Fig. 5 is corresponding constant current charge-discharge figure, is followed successively by 0g, 0.1g, 0.3g, 0.2g in Fig. 5 from left to right.As a result with
Cyclic voltammogram correspondence, soluble starch is 1 with the mass ratio of potassium permanganate:When 2.37, composite completes a discharge and recharge
The time of experience is most long.
Fig. 6 is the high rate performance figure of the soluble starch electrode material of correspondence different amounts.With the increase of electric current density,
Discount for four and decline to some extent, and the broken line when soluble starch consumption is 0.2g is in all the time the top, illustrates this
When electrode material high rate performance highest.
2nd, impact of the different carbon sources to specific capacitance
In order to illustrate impact of the carbon source soluble starch of the present invention to composite specific capacitance, glucose, sucrose have been selected in experiment
Carbon source as a comparison.Glucose, sucrose, the molecular formula of soluble starch are respectively C6H12O6, C12H22O11, (C6H10O5) n, carbochain
Increase successively.Fig. 7 is the cyclic voltammetry curve of the combination electrode material of different carbon source.Can be clearly observed from Fig. 7, Portugal
Area corresponding to grape sugar is minimum, and soluble starch is maximum as the corresponding area under the curve of carbon source material, and symmetry
It is good.Fig. 8 is the constant current discharge curve and high rate performance figure of correspondence carbon source electrode material.As a result show, soluble starch is completed
The time that once complete discharge and recharge needs is most long, and is shaped like isosceles triangle, and potential drop is also smaller, illustrates internal resistance
Very little, and the little transmission by beneficial to electronics of internal resistance, so as to improve specific capacitance value.Fig. 9 correspondence different carbon source electrode materials
High rate performance figure.From fig. 9, it can be seen that with the increase of electric current density, specific capacitance value is reducing, and the curve of soluble starch
The top is always positioned at, and no matter electric current density is much, and corresponding specific capacitance value is all maximum；Three decline of discounting becomes
Gesture generally remains consistent, illustrates different carbon sources, affects little to the high rate performance of material.But carbochain is longer, be more conducive to carrying
The specific capacitance of high material.
3rd, impact of the different surfaces activating agent to specific capacitance
In order to illustrate impact of the surfactant of the present invention to composite specific capacitance, nonionic surfactant has been selected
PEG 2000 is compared.Figure 10 is the cyclic voltammetry curve of different surfaces surfactant electrode material.Cyclic voltammogram shows, selects
Ctab surface activating agent, graphics area is bigger, and symmetry is more preferable.Figure 11 fills for the constant current of different surfaces surfactant electrode material
Discharge curve.Constant current charge-discharge figure shows, longer, discharge time longer meaning the time required to completing a circle discharge and recharge, CTAB
Specific capacitance value bigger.It can also be seen that from the nano material of PEG 2000, its potential drop is bigger than CTAB from figure,
Illustrate that internal resistance is larger, internal resistance is big, is unfavorable for the transmission of electronics, so as to affect specific capacitance value.Figure 12 is different surfaces activating agent electricity
The high rate performance figure of pole material.High rate performance figure show, with the increase of electric current density, specific capacitance reducing and, it is in office
Under what electric current density, CTAB possesses big specific capacitance all in top.
4th, cyclical stability test
MnO2/ C is in 8A g-1Under electric current density, the stability test of continuous 3000 circle is carried out.After test terminates, specific capacitance value
Conservation rate reached 82%, illustrate that cycle life is longer, and capacity retention is higher.Meanwhile, in 3000 circle test processs, storehouse
Human relations efficiency is always held at 90% ~ 100%.
In sum, hinge structure of the present invention has the effect that：
1st, the present invention is with potassium permanganate as oxidant and precursor, and CTAB is surfactant, and soluble starch is carbon source, manganese nitrate
For manganese source, the spherical nano material of class popped rice is synthesized under magnetic stirring, the material morphology of synthesis is homogeneous, short texture, than
Surface area is big；With excellent electrochemical capacitance performance, good cyclical stability, higher high rate performance and specific capacitance value are one
The combination electrode material of excellent performance is planted, has wide application front in fields such as hybrid vehicle, portable electric appts
Scape；
2nd, reaction condition is gentle（Without the need for N2）, preparation process is simple, without any virulent material participation reaction, more without Toxic
Matter is discharged, environmental protection；
3rd, the raw material of invention is cheap and easy to get, and low cost is conducive to large-scale production.
Description of the drawings
Fig. 1 is the infrared spectrogram of the manganese dioxide hybrid supercapacitor electrode material of present invention synthesis.
Fig. 2 is the XRD figure of the manganese dioxide hybrid supercapacitor electrode material of present invention synthesis.
Fig. 3 is the scanning electron microscope that the manganese dioxide hybrid supercapacitor electrode material of present invention synthesis amplifies different multiples
Figure.
Fig. 4 is the cyclic voltammetry curve of the soluble starch electrode material of different amounts.
Fig. 5 is the constant current charge-discharge curve of the soluble starch electrode material of different amounts.
Fig. 6 is the high rate performance figure of the soluble starch electrode material of different amounts.
Fig. 7 is the cyclic voltammetry curve of different carbon source electrode material.
Fig. 8 is the constant current discharge curve of different carbon source electrode material.
Fig. 9 is the high rate performance figure of different carbon source electrode material.
Figure 10 is the cyclic voltammetry curve of different surfaces surfactant electrode material.
Figure 11 is the constant current charge-discharge curve of different surfaces surfactant electrode material.
Figure 12 is the high rate performance figure of different surfaces surfactant electrode material.
Specific embodiment
Below by specific embodiment to the preparation method of manganese dioxide hybrid supercapacitor electrode material of the present invention and
Electrochemical capacitance performance is further described.
Embodiment 1
The soluble starch of 0.2g is added in the redistilled water of 100mL, intensification dissolves it, is cooled to room temperature, to
Wherein add 3mmol（0.4740g）Potassium permanganate and 25mg CTAB, under room temperature, in the magnetic stirring apparatuss of 90 ~ 120r/min
20 ~ 50min of upper stirring makes it fully react；The manganese nitrate solution of 20mL is added afterwards（Concentration is 0.1M）, maintain rotating speed to continue
3 ~ 5h of stirring, solution went from clear is changed into light brown, eventually forms dark-brown suspension, repeatedly washed with redistilled water, then
Water is sloughed with dehydrated alcohol, 50 ~ 70 DEG C of dryings, grinding obtains MnO2/ C composite.
Chemical property：It is 0.5A g in electric current density-1When, specific capacitance value is 235.2 F g-1。
Embodiment 2
The soluble starch of 0.3g is added in the redistilled water of 100mL, intensification dissolves it, is cooled to room temperature, to
Wherein add 3mmol（0.4740g）Potassium permanganate and 25mg CTAB, under room temperature, in the magnetic stirring apparatuss of 90 ~ 120r/min
Upper fully reaction, stirs 20 ~ 50min, is subsequently added into the manganese nitrate solution of 20mL（Concentration is 0.1M）, maintain rotating speed to continue to stir
3 ~ 5h, solution went from clear is changed into light brown, eventually forms dark-brown suspension, is repeatedly washed with redistilled water, then with nothing
Water-ethanol sloughs water, and 50 ~ 70 DEG C of dryings, grinding obtains MnO2/ C composite.
Chemical property：It is 0.5A g in electric current density-1When, specific capacitance value is 189.67 F g-1。
Embodiment 3
The soluble starch of 0.1g is added in the redistilled water of 100mL, intensification dissolves it, is cooled to room temperature, to
Wherein add 3mmol（0.4740g）Potassium permanganate and 25mg CTAB, under room temperature, in the magnetic stirring apparatuss of 90 ~ 120r/min
Upper fully reaction, stirs 20 ~ 50min, is subsequently added into the manganese nitrate solution of 20mL（Concentration is 0.1M）, maintain rotating speed to continue to stir
3 ~ 5h, solution went from clear is changed into light brown, eventually forms dark-brown suspension, is repeatedly washed with redistilled water, then with nothing
Water-ethanol sloughs water, and 50 ~ 70 DEG C of dryings, grinding obtains MnO2/ C composite.
Chemical property：It is 0.5A g in electric current density-1When, specific capacitance value is 156.22 F g-1。
Claims (5)
1. the synthetic method of a species popped rice spherical manganese dioxide hybrid supercapacitor electrode material, is that soluble starch is molten
Solution adds oxidant and surfactant in redistilled water, it is fully reacted under magnetic agitation；Add manganese nitrate molten
Liquid continues to stir, until solution went from clear is changed into light brown and eventually forms dark-brown suspension, obtains final product the spherical dioxy of class popped rice
Change manganese hybrid supercapacitor electrode material.
2. the synthetic method of species popped rice spherical manganese dioxide hybrid supercapacitor electrode material as claimed in claim 1,
It is characterized in that：The oxidant is potassium permanganate, and oxidant is 1.58 with the mass ratio of soluble starch:1~4.74:1.
3. the synthetic method of species popped rice spherical manganese dioxide hybrid supercapacitor electrode material as claimed in claim 1,
It is characterized in that：Surfactant is cetyl trimethylammonium bromide, and surfactant is with the mass ratio of soluble starch
0.083:1~0.25:1。
4. the synthetic method of species popped rice spherical manganese dioxide hybrid supercapacitor electrode material as claimed in claim 1,
It is characterized in that：The concentration of manganese nitrate solution is 0.1M, and manganese nitrate is 1.19 with the mass ratio of soluble starch:1~3.58:1.
5. the synthetic method of species popped rice spherical manganese dioxide hybrid supercapacitor electrode material as claimed in claim 1,
It is characterized in that：90 ~ the 120r/min of speed of magnetic agitation.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110921712A (en) * | 2019-12-11 | 2020-03-27 | 西京学院 | MnO (MnO)2Nano cage and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003123737A (en) * | 2001-10-10 | 2003-04-25 | Hitachi Maxell Ltd | Composite electrode material, method of manufacturing the same, and composite electrode using the composite electrode material |
| CN102730763A (en) * | 2012-06-29 | 2012-10-17 | 中国第一汽车股份有限公司 | Flower-like manganese dioxide electrode material for super-capacitor and preparation method thereof |
| CN103077835A (en) * | 2013-01-15 | 2013-05-01 | 上海大学 | Graphene load flower manganese dioxide (MnO2) composite material and ultrasonic synthetic method thereof |
| CN104362001A (en) * | 2014-11-28 | 2015-02-18 | 西北师范大学 | Method for preparing manganese dioxide/graphene/porous carbon (MnO2/rGO/C) composite material and application of MnO2/rGO/C composite material to supercapacitor as electrode material |
| CN104392849A (en) * | 2014-11-20 | 2015-03-04 | 中南大学 | Manganese dioxide/ con composite material preparing method |
| CN104409219A (en) * | 2014-11-28 | 2015-03-11 | 西北师范大学 | Preparation method for hexagonal manganese dioxide nanosheet material and application of hexagonal manganese dioxide nanosheet material as electrode material of supercapacitor |
| CN105084422A (en) * | 2014-05-19 | 2015-11-25 | 中国科学院过程工程研究所 | Three-dimensional multi-structural cobaltosic oxide/carbon/manganese dioxide composite micro-nanomaterial and in-situ controllable preparation method thereof |
-
2016
- 2016-12-28 CN CN201611237685.7A patent/CN106601496B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003123737A (en) * | 2001-10-10 | 2003-04-25 | Hitachi Maxell Ltd | Composite electrode material, method of manufacturing the same, and composite electrode using the composite electrode material |
| CN102730763A (en) * | 2012-06-29 | 2012-10-17 | 中国第一汽车股份有限公司 | Flower-like manganese dioxide electrode material for super-capacitor and preparation method thereof |
| CN103077835A (en) * | 2013-01-15 | 2013-05-01 | 上海大学 | Graphene load flower manganese dioxide (MnO2) composite material and ultrasonic synthetic method thereof |
| CN105084422A (en) * | 2014-05-19 | 2015-11-25 | 中国科学院过程工程研究所 | Three-dimensional multi-structural cobaltosic oxide/carbon/manganese dioxide composite micro-nanomaterial and in-situ controllable preparation method thereof |
| CN104392849A (en) * | 2014-11-20 | 2015-03-04 | 中南大学 | Manganese dioxide/ con composite material preparing method |
| CN104362001A (en) * | 2014-11-28 | 2015-02-18 | 西北师范大学 | Method for preparing manganese dioxide/graphene/porous carbon (MnO2/rGO/C) composite material and application of MnO2/rGO/C composite material to supercapacitor as electrode material |
| CN104409219A (en) * | 2014-11-28 | 2015-03-11 | 西北师范大学 | Preparation method for hexagonal manganese dioxide nanosheet material and application of hexagonal manganese dioxide nanosheet material as electrode material of supercapacitor |
Non-Patent Citations (4)
| Title |
|---|
| HUAILONG LI等: ""MnO2 nanoflakes/hierarchical porous carbon nanocomposites for high-performance supercapacitor electrodes"", 《ELECTROCHIMICA ACTA》 * |
| SHIJIN ZHU等: ""Flower-like MnO2 decorated activated multihole carbon as high-performance asymmetric supercapacitor electrodes"", 《MATERIALS LETTERS》 * |
| YANMEI PAN等: ""Facile synthesis of mesoporous MnO2/C spheres for supercapacitor electrodes"", 《CHEMICAL ENGINEERING JOURNAL》 * |
| 王红强等: ""淀粉还原制备纳米MnO2超级电容器电极材料"", 《化工新型材料》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110921712A (en) * | 2019-12-11 | 2020-03-27 | 西京学院 | MnO (MnO)2Nano cage and preparation method and application thereof |
| CN110921712B (en) * | 2019-12-11 | 2022-06-07 | 西京学院 | MnO (MnO)2Nano cage and preparation method and application thereof |
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