CN106044861A - Preparation method for three-dimensional branched manganese dioxide nano-material - Google Patents
Preparation method for three-dimensional branched manganese dioxide nano-material Download PDFInfo
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- CN106044861A CN106044861A CN201610352477.5A CN201610352477A CN106044861A CN 106044861 A CN106044861 A CN 106044861A CN 201610352477 A CN201610352477 A CN 201610352477A CN 106044861 A CN106044861 A CN 106044861A
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- manganese dioxide
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000002244 precipitate Substances 0.000 claims abstract description 20
- 239000011572 manganese Substances 0.000 claims abstract description 17
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 238000009415 formwork Methods 0.000 claims description 45
- 239000000463 material Substances 0.000 claims description 22
- 150000002697 manganese compounds Chemical class 0.000 claims description 20
- 239000003990 capacitor Substances 0.000 claims description 18
- 239000012286 potassium permanganate Substances 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 125000000524 functional group Chemical group 0.000 claims description 7
- 239000006260 foam Substances 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 230000002209 hydrophobic effect Effects 0.000 claims description 5
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical group Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 3
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 3
- 239000000839 emulsion Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 125000001302 tertiary amino group Chemical group 0.000 claims description 3
- 230000000994 depressogenic effect Effects 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 125000003368 amide group Chemical group 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 239000007772 electrode material Substances 0.000 abstract description 18
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000003792 electrolyte Substances 0.000 abstract description 4
- 238000005406 washing Methods 0.000 abstract description 2
- 238000005119 centrifugation Methods 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- 238000001132 ultrasonic dispersion Methods 0.000 abstract 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 16
- 238000000034 method Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002060 nanoflake Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 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 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 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 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000003001 depressive effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- UBXWAYGQRZFPGU-UHFFFAOYSA-N manganese(2+) oxygen(2-) titanium(4+) Chemical compound [O--].[O--].[Ti+4].[Mn++] UBXWAYGQRZFPGU-UHFFFAOYSA-N 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000007557 optical granulometry Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000001507 sample dispersion Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 239000002341 toxic gas Substances 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
Abstract
The invention provides a preparation method for a three-dimensional branched manganese dioxide nano-material and belongs to the technical field of electrode materials of supercapacitors. According to the preparation method, the probability of contact between the manganese dioxide nano-material and an electrolyte can be increased, so that the electrochemical properties of the manganese dioxide nano-material are improved. The preparation method for the three-dimensional branched manganese dioxide nano-material, provided by the invention, comprises the steps: dispersing amphiphilic organic molecules into water in an ultrasonic dispersion manner, adjusting the pH value of the dispersion, and carrying out placing at room temperature, so as to obtain an organic template solution; sequentially adding a solution of manganese-containing compounds into the organic template solution, carrying out uniform stirring and mixing, then, carrying out a reaction for 1 to 10 hours, and carrying out centrifugation, so as to obtain brown precipitates; and washing, drying and heating the brown precipitates, thereby obtaining the three-dimensional branched manganese dioxide nano-material after organic templates are removed. The three-dimensional branched manganese dioxide nano-material can be applied to the preparation of the electrode materials of the supercapacitors and electrodes of the supercapacitors.
Description
Technical field
The present invention relates to electrode material for super capacitor technical field, particularly relate to a kind of three-dimensional branched manganese dioxide nano
The preparation method of material.
Background technology
The growth of world population and the fast development of industry, in the urgent need to providing the more energy, currently mainly rely on stone
The burning of the fossil resources such as oil, coal, natural gas provides.On the one hand, the deposit of fossil resource is limited, it is difficult to regeneration；The opposing party
Face, discharges substantial amounts of toxic gas while these fossil-fueleds provide energy, brings serious problem of environmental pollution.
Therefore, effective way that clean, that continuable energy technology is solution economic development and environment protection contradiction is developed.Super electricity
Container appear as people reduce tradition directly utilizing of fossil energy provide excellent opportunity.
Ultracapacitor has available big electric current and carries out fast charging and discharging, the feature having extended cycle life, and this is also its difference
One of important feature in current main-stream accumulator-battery, at solar wind-energy generating, electric automobile, electronics, electromagnetism high power
The fields such as weaponry illustrate wide application prospect.According to the difference of energy storage principle, ultracapacitor is divided into electric double layer electricity
Container and Faraday pseudo-capacitance device two kinds.Owing to Faraday pseudo-capacitance device may utilize body phase atom, at identical electrode surface area
Under, the capacitance of Faraday pseudo-capacitance device is big 1-2 the order of magnitude than electric double layer capacitance, therefore receives much concern.
As a new technology, ultracapacitor still suffer from present with high costs, capacity is less than normal, the life-span is on the low side lacks
Point, its bottleneck is still electrode material.Ruthenium-oxide is the combination property generally acknowledged in the metal oxide electrode material of research at present
Excellent electrode material, but because its cost is higher and needs to reduce its actual application by Strong acidic electrolyte environment
It is worth.The high performance of lower cost materials is one of important directions of functional material development.Manganese oxide low price, and have non-
The highest theory, than electric capacity, is preferable fake capacitance electrode material, but the ratio electric capacity that can reach at present differs relatively with its theoretical value
Greatly.How to make manganese oxide material reach higher chemical property while not improving cost, become current researcher
The target striven for.
At present, can be by the high material of conductivity that adulterates in manganese oxide (noble metal or the Graphene etc. such as such as gold, silver
Material with carbon element) or direct regulation and control manganese oxide carry in the mode of the upper deposition of conductive substrates (such as silicon, CNT, porous carbon etc.)
High its compares electric capacity.But problematically, using aforesaid way to improve chemical property is to enter based on the quality of manganese oxide in mixture
Row calculates.But, owing in electrode, the content of manganese oxide is relatively low, for whole electrode, its electrochemical properties
Raising very limited.Therefore, the preparation method of a kind of nano material of manganese dioxide with high-specific surface area, energy how are provided
Enough increase the contact probability of nano material of manganese dioxide and electrolyte, thus improving its electrochemical properties will be that this area is faced
Important topic.
Summary of the invention
It is an object of the invention to provide the preparation method of the branched nano material of manganese dioxide of a kind of three-dimensional, by increasing capacitance it is possible to increase two
Manganese oxide nanometer material and the contact probability of electrolyte, thus improve its electrochemical properties.
An aspect of of the present present invention provides the preparation method of the branched nano material of manganese dioxide of a kind of three-dimensional, including:
By amphipathic organic molecule ultrasonic disperse in water, regulate pH value, be placed in room temperature and place, obtain organic formwork molten
Liquid；
To contain manganese compound solution to be added sequentially in described organic formwork solution, after mixing to be mixed, 1-10 is little in reaction
Time, it is centrifuged and obtains tan precipitate；
Described tan precipitate is washed, is dried and heats, after organic formwork to be removed, obtain three-dimensional branched titanium dioxide
Manganese nano material.
Preferably, described containing in manganese compound solution and described organic formwork solution containing manganese compound and organic formwork
Mol ratio is 10:1-1:30.
Optionally, described is potassium permanganate and manganese nitrate containing manganese compound.
Preferably, the mol ratio of described potassium permanganate and described manganese nitrate is 2:1-2:10.
Optionally, by amphipathic organic molecule ultrasonic disperse in water after, pH value is adjusted in the range of 3-9.
Optionally, one end of described amphipathic organic molecule is that the other end is for containing containing the hydrophobic units that can form hydrogen bond
Having the hydrophilic unit of functional groups, wherein, described functional groups is selected from primary amine groups, tertiary amine groups, guanidine radicals, imidazole radicals and carboxyl
In at least one.
Optionally, described tan precipitate is heated 2-10 hour at a temperature of 300 DEG C-600 DEG C, described organic to remove
Template.
Another aspect provides a kind of branched titanium dioxide of three-dimensional as according to any one of technique scheme
The preparation method branched nano material of manganese dioxide of preparation-obtained three-dimensional of manganese nano material.
Another aspect of the invention provides a kind of three-dimensional as described in technique scheme branched manganese dioxide nano material
Expect the application in prepared by electrode of super capacitor.
It is yet another aspect of the present invention to provide the preparation method of a kind of electrode of super capacitor, including:
By three-dimensional branched nano material of manganese dioxide, acetylene black, the ratio of ptfe emulsion 80:15:5 in molar ratio
Mixing, the rear ethanol that adds to be mixed stirs, and dries；
After drying, the powder that obtains is coated in two panels nickel foam, with hydraulic press with the pressure of 10MPa by two panels nickel foam
Pressure is as working electrode, and auxiliary electrode is platinum filament, and reference electrode is saturated calomel electrode.
The invention provides the preparation method of the branched nano material of manganese dioxide of a kind of three-dimensional, compared to prior art
Speech, the method, in the presence of one-dimensional organic formwork, is existed by the molecular recognition of organic formwork, catalytic action induced manganese dioxide
Template surface nucleation, growth, then assemble under organic and inorganic interface interaction drives, construct by the nano flake group distorted
The manganese bioxide material of the three-dimensional branched structure that dress is formed.The branched nano material of manganese dioxide of three-dimensional prepared by the method
Having the specific surface area of multilevel ordered three dimensional structure and superelevation, specific surface area is up to 250m2g-1, much larger than by nanoparticle
(52-108m2g-1), nanometer rods (100-150m2g-1), nanometer sheet (23-43m2g-1) etc. as the ratio electric capacity of electrode material, have
Excellent chemical property, using it as electrode material, can obtain up to 430F g-1Ratio electric capacity, good resistance to height sweeps speed
And cyclical stability, higher than the common electrode material being made up of pure manganese dioxide.The method is at room temperature, normal pressure and weakly acidic pH ring
Having synthesized three-dimensional branched nano material of manganese dioxide under border, whole building-up process has feature simple, energy-conservation, eco-friendly.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope of the embodiment of the present invention branched nano material of manganese dioxide of preparation-obtained three-dimensional
Photo；
Fig. 2 A is the nitrogen adsorption-desorption of the embodiment of the present invention branched nano material of manganese dioxide of preparation-obtained three-dimensional
Curve；
Fig. 2 B is the BJH pore volume distribution of the embodiment of the present invention branched nano material of manganese dioxide of preparation-obtained three-dimensional
Curve；
Fig. 3 A is making with the branched nano material of manganese dioxide of three-dimensional for preparing of being provided of the embodiment of the present invention
The cyclic voltammetry curve of electrode of super capacitor；
The super capacitor electrode that the branched nano material of manganese dioxide of three-dimensional that Fig. 3 B is provided by the embodiment of the present invention makes
Ratio electric capacity-sweep speed the curve of pole；
Fig. 4 by the embodiment of the present invention provided with the branched nano material of manganese dioxide of three-dimensional for preparing make super
Ratio electric capacity-cycle-index the curve of 2500 circulations of level electrode for capacitors.
Detailed description of the invention
Technical scheme in the embodiment of the present invention will be clearly and completely described below, it is clear that described enforcement
Example is only a part of embodiment of the present invention rather than whole embodiments.Based on the embodiment in the present invention, this area is common
The every other embodiment that technical staff is obtained under not making creative work premise, broadly falls into the model of present invention protection
Enclose.
Embodiments provide the preparation method of the branched nano material of manganese dioxide of a kind of three-dimensional, including:
S1: by amphipathic organic molecule ultrasonic disperse in water, regulates pH value, is placed in room temperature and places, obtains organic formwork
Solution；
In this step, one-dimensional organic formwork is built first with amphipathic self assembly of organic molecules.Concrete, by two
After parent's property organic molecule ultrasonic disperse is in water, regulating system pH to weakly acidic pH, place static a period of time, obtaining this has
Machine template solution.In this step, select the mode being dispersed in water by amphipathic organic molecule to obtain one-dimensional organic formwork
It is in order to obtained one-dimensional organic formwork solution is then able to preferably mix with the solution containing manganese compound, to be formed
Homogeneous 3-D nano, structure.
S2: will contain manganese compound solution and be added sequentially in described organic formwork solution, after mixing to be mixed, reacts 1-10
Hour, it is centrifuged and obtains tan precipitate；
In this step, in order to obtain tan precipitate, containing manganese compound solution, to be added sequentially to described organic formwork molten
In liquid, after mixing, react a period of time, to ensure fully to react with organic formwork containing manganese compound.It is understood that it is anti-
Between Ying Shi depending on the abundant degree of reaction containing manganese compound Yu organic formwork, it can be 2,3,4,5,6,7,8,9 hours
Or other the arbitrary point value in above-mentioned scope.
S3: wash described tan precipitate, be dried and heat, after organic formwork to be removed, obtains three-dimensional branched two
Manganese oxide nanometer material.
In this step, tan precipitate is washed successively, be dried and heat.Wherein, washing is the most anti-in order to remove
Answer containing manganese compound, heating is to remove organic formwork.
In one embodiment of this invention, described containing closing containing manganese in manganese compound solution and described organic formwork solution
The mol ratio of thing and organic formwork is 10:1-1:30.In the present embodiment, in order to ensure filling containing manganese compound and organic formwork
Divide reaction, also for ensureing that the pattern of preparation-obtained nano material of manganese dioxide, structure (hole dimension, specific surface area) reach
Expection standard, and there is excellent electrochemical properties (than electric capacity, resistance to high sweeping speed, cyclical stability), to containing in the present embodiment
Manganese compound is optimized with the mol ratio of organic formwork, and i.e. mol ratio is in the range of 10:1-1:30.May be appreciated
It is, by the preparation-obtained nano material of manganese dioxide of mol ratio in above-mentioned scope at aspects such as pattern, structure, electrochemical properties
All meet the expected requirements.Preferably, the molar ratio containing manganese compound and organic formwork as can be 10:1,5:1,1:1,1:5,
1:10,1:15,1:20,1:25,1:30 etc..It is understood that the mol ratio containing manganese compound and organic formwork is not limited to
In above-mentioned cited, as long as meeting above-mentioned range of condition.
In a preferred embodiment of above-described embodiment, described is potassium permanganate and manganese nitrate containing manganese compound.In this reality
Executing in example, the redox reaction mainly by potassium permanganate (+7 valency) and manganese nitrate (+divalent) obtains manganese dioxide (+4
Valency), it is to be understood that utilize the manganese sulfate with valence state, manganese acetate or manganese chloride to replace manganese nitrate to react also with potassium permanganate
It is likely to be obtained the material of similar structures.In theory, both can be prepared by the reduction of value Mn (such as potassium permanganate),
Can also be obtained by the oxidation of lower valency manganese (such as manganese nitrate).Need exist for explanation, for the reduction of value Mn
For preparation, more need to consider reduction reaction rate, if reduction reaction rate is relatively slow, then can not obtain in the application
There is the nano material of manganese dioxide of the three-dimensional branched structure of rule, such as, reduce potassium permanganate with glucose, formic acid etc..
In a preferred embodiment of above-described embodiment, the mol ratio of described potassium permanganate and described manganese nitrate is 2:1-2:
10.In the present embodiment, different proportionings only can produce impact to the homogeneity of reaction rate and product morphology, compares at some
Under example, in addition to three-dimensional branched structure, it is also possible to generate the material of other structure of certain proportion, but this has no effect on and obtains this Shen
The manganese dioxide of the three-dimensional branched structure please provided.
In one embodiment of this invention, by amphipathic organic molecule ultrasonic disperse in water after, pH value is adjusted to 3-9
In the range of.In the present embodiment, pH value is adjusted in the range of 3-9, it can be ensured that the overall ring at weakly acidic pH of reaction system
React under border, to ensure that whole building-up process has eco-friendly feature.It is understood that can by pH value regulation 4,5,6,
7,8 other arbitrary point value not etc. or in above-mentioned scope.
In one embodiment of this invention, one end of described amphipathic organic molecule is containing the hydrophobic list that can form hydrogen bond
Unit, the other end is the hydrophilic unit of functional groups, wherein, can be formed the hydrophobic units of hydrogen bond by NH, O etc., can by primary amine groups,
The hydrophilic unit of at least one functional groups composition in tertiary amine groups, guanidine radicals, imidazole radicals, carboxyl.In the present embodiment, pass through
Hydrophobe effect and intermolecular hydrogen bonding effect etc. build periphery and are coated with the one-dimensional organic formwork of functional groups, so can pass through
Regulate hydrophilic, the composition of hydrophobic part, structure or assembling condition regulates and controls the size of organic formwork, pattern and surface nature etc..
In one embodiment of this invention, described tan precipitate is heated 2-10 hour at a temperature of 300 DEG C-600 DEG C,
To remove described organic formwork.In the present embodiment, owing to organic formwork has volatility, therefore select tan precipitate at height
Heat under temperature, effectively to remove organic formwork.Selecting to carry out heating at a temperature of 300 DEG C-600 DEG C is to remove
Can keep the integrity of three-dimensional branched manganese dioxide nano structure while organic formwork, such as, high-temperature temperature can be 350
DEG C, 400 DEG C, 450 DEG C, 500 DEG C, 550 DEG C or should in the range of other arbitrary point value.It is understood that for adding
The heat time, in the application and be not specifically limited, as long as can completely remove by organic formwork, infrared light can be passed through here
1600-1700cm in spectrum-1Whether the INFRARED ABSORPTION of interval amide I band disappears and judges.Such as, heating-up temperature can be 3,4,5,6,
7,8,9 hours other arbitrary point values not etc. or in above-mentioned scope.
Another embodiment of the present invention provides a kind of branched titanium dioxide of three-dimensional as according to any one of above-described embodiment
The preparation method branched nano material of manganese dioxide of preparation-obtained three-dimensional of manganese nano material.It is prepared into by the embodiment of the present invention
To the branched nano material of manganese dioxide of three-dimensional there is the specific surface area of multilevel ordered three dimensional structure and superelevation, specific surface area is high
Reach 250m2g-1, much larger than by nanoparticle (52-108m2g-1), nanometer rods (100-150m2g-1), nanometer sheet (23-43m2g-1)
Deng the ratio electric capacity as electrode material, there is the chemical property of excellence, using it as electrode material for super capacitor, can obtain
Up to 430F g-1Ratio electric capacity, good resistance to height sweeps speed and cyclical stability, higher than common by pure manganese bioxide material structure
The electrode of super capacitor become.
One more embodiment of the present invention provides a kind of three-dimensional as described in above-described embodiment branched manganese dioxide nano material
Expect the application in prepared by electrode of super capacitor.The three-dimensional branched manganese dioxide nano material prepared by the embodiment of the present invention
Material, therefore can be as super owing to having multilevel ordered three dimensional structure, the specific surface area of superelevation and the chemical property of excellence
Level capacitor electrode material, when it is as electrode material, can obtain up to 430F g-1Ratio electric capacity, good resistance to height sweeps speed
And cyclical stability, therefore can be used for preparing the electrode of ultracapacitor.
Another embodiment of the present invention provides the preparation method of a kind of electrode of super capacitor, including:
S1: by three-dimensional branched nano material of manganese dioxide, acetylene black, ptfe emulsion 80:15:5 in molar ratio
Ratio mixes, and the rear ethanol that adds to be mixed stirs, and dries；
S2: after drying, the powder that obtains is coated in two panels nickel foam, with hydraulic press with the pressure of 10MPa by two panels foam
Nickel is depressed as working electrode, and auxiliary electrode is platinum filament, and reference electrode is saturated calomel electrode.
The above embodiment of the present invention lists a kind of branched dioxy of the three-dimensional utilizing the above embodiment of the present invention to prepare
Change the manganese nano material method preparing electrode of super capacitor as electrode material.Owing to the embodiment of the present invention prepares
Three-dimensional branched nano material of manganese dioxide has multilevel ordered three dimensional structure, the specific surface area of superelevation and the electrochemistry of excellence
Performance, therefore as electrode material for time prepared by electrode of super capacitor, can obtain the electrode with excellent electrochemical performance.
In order to become apparent from introducing the three-dimensional branched nano material of manganese dioxide of one that the embodiment of the present invention is provided in detail
Preparation method, illustrate below with reference to specific embodiment.
Embodiment 1
First, by amphipathic organic molecule ultrasonic disperse in water, regulation pH value, to 3, is placed in room temperature and places, obtain organic
Template solution；Subsequently, potassium permanganate solution and manganese nitrate solution are joined in described organic formwork solution, mixing to be mixed
After, react 1-3 hour, be centrifuged and obtain tan precipitate；Finally, described tan precipitate is washed, is dried and heats, to be removed
After organic formwork, obtain three-dimensional branched nano material of manganese dioxide 1.
Embodiment 2
First, by amphipathic organic molecule ultrasonic disperse in water, regulation pH value, to 6, is placed in room temperature and places, obtain organic
Template solution；Subsequently, potassium permanganate solution and manganese nitrate solution are joined in described organic formwork solution, mixing to be mixed
After, react 4-6 hour, be centrifuged and obtain tan precipitate；Finally, described tan precipitate is washed, is dried and heats, to be removed
After organic formwork, obtain three-dimensional branched nano material of manganese dioxide 2.
Embodiment 3
First, by amphipathic organic molecule ultrasonic disperse in water, regulation pH value, to 9, is placed in room temperature and places, obtain organic
Template solution；Subsequently, potassium permanganate solution and manganese nitrate solution are joined in described organic formwork solution, mixing to be mixed
After, react 7-10 hour, be centrifuged and obtain tan precipitate；Finally, described tan precipitate is washed, is dried and heats, wait to remove
After removing organic formwork, obtain three-dimensional branched nano material of manganese dioxide 3.
By pattern, the structural table of the preparation-obtained three-dimensional of above-described embodiment 1-3 branched nano material of manganese dioxide 1-3
Levy, chemical property the most identical, therefore, as a example by the branched nano material of manganese dioxide of three-dimensional 2 that will obtain by embodiment 2 below
It is specifically described.
Embodiment 4
The pattern of three-dimensional branched nano material of manganese dioxide and structural characterization
High resolution transmission electron microscopy, model: JEM-2100UHR, instrument manufacturer facility man: NEC (JEOL), add
Speed voltage: 200kV；
The present embodiment combines high-resolution transmission microscopy and energy depressive spectroscopy observes three-dimensional branched manganese dioxide nano material
The pattern of material and structure, concrete, by sample dispersion in ethanol, drop on the copper mesh being coated with carbon film, utilize special after drying
Specimen holder put into sample room, evacuation, regulate suitable resolution and focal length, select suitable time of exposure, shoot image.
By in Fig. 1 it can be seen that the nano flake of manganese dioxide is to assemble, along one-dimensional organic formwork, the three-dimensional that formed to prop up
Changing structure, found by the transmission electron microscope photo analysis amplified, nanometer sheet is twisted state, and the thickness of single nano flake is less than
1 nanometer, under the regulation and control of one-dimensional organic formwork, ordered fabrication is formed.Just because of this microstructure, impart manganese dioxide
The highest specific surface area and electrochemical surface area.
Embodiment 5
The BET specific surface area test of three-dimensional branched nano material of manganese dioxide
Use Autosorb-6B type Physisorption Analyzer to analyze, sample 200 DEG C of degassings under vacuo are processed, then
Sample is put in the cold-trap added with liquid nitrogen, given P/P0 value, just can be measured by the gas-distribution pipe of constant temperature after reaching adsorption equilibrium
Adsorption volume V.So by the measured value of a series of P/P0 and V, obtain multiple data point, these data points are coupled together
To absorption isotherm, otherwise reducing vacuum, abjection adsorbed gas can obtain being desorbed line, is calculated ratio after bringing fractured model into
Surface area and pore-size distribution information, i.e. BJH curve.
By in Fig. 2 A it can be seen that three-dimensional branched nano material of manganese dioxide shows the feature of IV type isothermal curve,
Occurring in that lag loop in the range of relative pressure 0.4-1.0, show to mainly contain narrow slit-like hole in material, this also enters one
It is to be formed along one-dimensional organic formwork stacking by patch unit that step demonstrates three-dimensional branched manganese bioxide material.Can be seen by Fig. 2 B
Going out, the aperture of three-dimensional branched manganese bioxide material is at about 3-8nm.
Embodiment 6
Three-dimensional branched manganese bioxide material is as the ratio electric capacity-sweep speed tracing analysis of electrode material for super capacitor
By Fig. 3 A it can be seen that at scanning speed 5-100mV s-1In the range of, it is long that its cyclic voltammetry curve all presents approximation
Square, even if the most significantly distorting under height sweeps speed, show the branched manganese dioxide of three-dimensional that the embodiment of the present invention is prepared into
Nano material electrode has good capacitance characteristic.Fig. 3 B is the ratio electric capacity-sweep of three-dimensional branched nano material of manganese dioxide electrode
Retouching rate curve, more clearly demonstrate this point, the most three-dimensional branched nano material of manganese dioxide electrode has higher ratio
Electric capacity and good resistance to height sweep speed.
Embodiment 7
Three-dimensional branched manganese bioxide material is as electrode material for super capacitor ratio electric capacity-circulation after 2500 circulations
Number of times is analyzed
The present embodiment is with 5mV s-1Scanning speed under, manganese bioxide material branched to above-mentioned three-dimensional has carried out 2500 times following
Ring scans, and as shown in Figure 4, is simply declined slightly than electric capacity, and after 2500 scanning than the conservation rate of electric capacity about 95%,
The most provable prepared three-dimensional branched manganese bioxide material has good cyclical stability as electrode of super capacitor.
Claims (10)
1. the preparation method of the branched nano material of manganese dioxide of three-dimensional, it is characterised in that including:
By amphipathic organic molecule ultrasonic disperse in water, regulate pH value, be placed in room temperature and place, obtain organic formwork solution；
Manganese compound solution will be contained be added sequentially in described organic formwork solution, after mixing to be mixed, react 1-10 hour, from
Gains in depth of comprehension are to tan precipitate；
Described tan precipitate is washed, is dried and heats, after organic formwork to be removed, obtain three-dimensional branched manganese dioxide and receive
Rice material.
Preparation method the most according to claim 1, it is characterised in that described containing manganese compound solution and described organic formwork
The mol ratio containing manganese compound and organic formwork in solution is 10:1-1:30.
Preparation method the most according to claim 1 and 2, it is characterised in that described is potassium permanganate and nitre containing manganese compound
Acid manganese.
Preparation method the most according to claim 3, it is characterised in that described potassium permanganate and the mol ratio of described manganese nitrate
For 2:1-2:10.
Preparation method the most according to claim 1, it is characterised in that by amphipathic organic molecule ultrasonic disperse in water
After, pH value is adjusted in the range of 3-9.
Preparation method the most according to claim 1, it is characterised in that one end of described amphipathic organic molecule can for containing
Forming the hydrophobic units of hydrogen bond, the other end is the hydrophilic unit containing functional groups, and wherein, described functional groups is selected from primary
At least one in amido, tertiary amine groups, guanidine radicals, imidazole radicals and carboxyl.
Preparation method the most according to claim 1, it is characterised in that by described tan precipitate the temperature of 300 DEG C-600 DEG C
Degree lower heating 2-10 hour, to remove described organic formwork.
8. prepared by the preparation method of the branched nano material of manganese dioxide of the three-dimensional as according to any one of claim 1-7
The branched nano material of manganese dioxide of three-dimensional obtained.
9. the branched nano material of manganese dioxide of three-dimensional as claimed in claim 8 answering in prepared by electrode of super capacitor
With.
10. the preparation method of an electrode of super capacitor, it is characterised in that including:
Three-dimensional branched nano material of manganese dioxide, acetylene black, the ratio of ptfe emulsion 80:15:5 in molar ratio are mixed
Closing, the rear ethanol that adds to be mixed stirs, and dries；
The powder obtained after drying is coated in two panels nickel foam, two panels nickel foam is depressed with the pressure of 10MPa with hydraulic press
As working electrode, auxiliary electrode is platinum filament, and reference electrode is saturated calomel electrode.
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| CN109867306B (en) * | 2017-12-05 | 2022-02-15 | 中国科学院大连化学物理研究所 | Low-temperature preparation method of mesoporous manganese dioxide nanosheets |
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