CN104392848A - Method for preparing element doped manganese dioxide electrode materials for super-capacitors - Google Patents
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000007772 electrode material Substances 0.000 title claims abstract description 14
- 239000003990 capacitor Substances 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 11
- 229910052796 boron Inorganic materials 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 230000035484 reaction time Effects 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- -1 boron ion Chemical class 0.000 claims abstract description 3
- 239000012266 salt solution Substances 0.000 claims abstract description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 10
- 239000006227 byproduct Substances 0.000 claims description 8
- 239000011572 manganese Substances 0.000 claims description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 7
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- 229940071125 manganese acetate Drugs 0.000 claims description 6
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 6
- 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 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 229910021538 borax Inorganic materials 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- 238000006479 redox reaction Methods 0.000 claims description 4
- 239000004328 sodium tetraborate Substances 0.000 claims description 4
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 4
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 239000007795 chemical reaction product Substances 0.000 abstract 2
- 150000002696 manganese Chemical class 0.000 abstract 2
- 230000001351 cycling effect Effects 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000001291 vacuum drying Methods 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 239000004744 fabric Substances 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000011149 active material Substances 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- NOMICGATVHRDNY-UHFFFAOYSA-N [Mn].Cl(=O)(=O)O Chemical compound [Mn].Cl(=O)(=O)O NOMICGATVHRDNY-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000002800 charge carrier Substances 0.000 description 2
- 229910052729 chemical element Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 230000005536 Jahn Teller effect Effects 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000002772 conduction electron Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000012876 topography Methods 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
- H01G11/46—Metal oxides
-
- 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
- H01G11/84—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
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- 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)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention discloses a method for preparing element doped manganese dioxide electrode materials for super-capacitors and belongs to the technical field of electrode materials. Particularly, the method comprises adding a borate solution and a divalent manganese salt solution into a potassium permanganate solution successively to be subjected to hydrothermal reaction, wherein the molar ratio between the divalent manganese salt and the potassium permanganate is 1: (0.5-5), the boron ion concentration is 0.001M-5M, the reaction temperature is in a range of 60 DEG C to 160 DEG C, and the reaction time is 1h-24h; washing reaction products with ethyl alcohol and de-ionized water respectively and performing vacuum drying on the washed reaction products for 4h to 24h in the temperature ranging from 60 DEG C to 120 DEG C. According to the method, the reaction condition is mild, the production cost is low, the technical route is simple and convenient, the activity and the specific capacity of the prepared manganese dioxide materials are high, the capacitive performance is good, and the cycling stability is high.
Description
Technical field
The invention belongs to electrode material technical field, be specifically related to a kind of preparation method of element-doping manganese bioxide electrode material for super capacitor.
Background technology
Ultracapacitor can meet the needs of the high-power outputs such as electric automobile startup, acceleration, also can be used for the occasion that the low-power consumption such as circuit components, compact electric apparatus exports, and is the more advanced energy storage mode of a class.From the angle of electrode material, now widely used is material with carbon element (acetylene black, carbon nano-tube and Graphene etc.), organic conductive polymer and transition metal oxide (RuO
2, MnO
x, NiO
xand CoO
xdeng).Material with carbon element is applied the earliest, is also current industrialization the most successfully electrode material for super capacitor.But the charge storage of material with carbon element relies on surface electric double layer structure and realizes, and its storage capacity is lower; Organic conductive polymer is in charge and discharge cycles process, and structure disperses is large, poor stability, causes capability retention low; There is faraday's reaction at Cathode/Solution Interface in metal oxide, the faraday's electric capacity produced will much larger than the electric double layer capacitance of carbon material surface, and service life cycle is longer than organic conductive polymer.Therefore, metal oxide becomes the study hotspot of electrode material for super capacitor.Based on the consideration of the many factors such as cost and environmental protection, manganese dioxide is especially noticeable.
Although MnO
2theoretical ratio capacitance up to 1370 F/g, but as a kind of semi-conducting material, the ability of block manganese dioxide conduction electron is also bad.During as electrode material for super capacitor, actual capacity is far smaller than its theoretical discharge capacity, such as, and powder MnO
2ratio capacitance scope is mostly 100-300 F/g.Trace it to its cause, mainly the embedding of charge carrier (proton/alkali ion) and deintercalation and Mn related to this
4+/ Mn
3+the time compole of redox reaction is short, and charge carrier has little time, to active material diffusion inside, to only have the sub-fraction MnO of electrode surface
2redox reaction occurs, and " a large amount of " inner active material does not participate in reacting [P. Simon et. al, Nat. Mater. 7 (2008) 845-854].For overcoming this drawback, MnO is put forth effort in much research
2doping vario-property.Such as the material with carbon element of high specific surface area is directly added in the preparation system of manganese dioxide, obtained manganese dioxide/carbon composite.This material contributes to the contact resistance reducing electrode, improve the dynamics invertibity of electrode, improve the utilance of active material, thus add the specific capacity [A. Sumboja et.al, Adv. Mater. 25 (2013) 2809 – 2815] of electrode.More advanced is chemical element doping.Element doping can change the ion in manganese oxide octahedral sieve skeleton structure or tunnel, improves stability and oxygen Evolution overpotential.At present cation doping [J.-H. Moon et. al, Electrochim. Acta 134 (2014) 92-99] is mainly concentrated on to the research of chemical element doping, namely carry out the Mn of Substitute For Partial octahedral site with metal cation
3+, control the oxidation state of manganese, cause unit cell volume to shrink, alleviate the distortion degree of lattice, and then suppress Jahn-Teller effect, improve electrode cycle performance.But to MnO
2the doping vario-property research of nonmetalloid is not yet seen in report.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of element-doping manganese bioxide electrode material for super capacitor.Concrete grammar is:
First, potassium permanganate, manganous salt and borate are dissolved in deionized water respectively; Borate solution and manganous salt solution are joined in liquor potassic permanganate successively.The mol ratio of manganous salt and potassium permanganate is 1:0.5-5; Boron ion concentration is 0.001-5M; Manganous salt comprises manganese sulfate, manganese nitrate, manganese acetate, manganese chloride; Borate comprises boric acid, borax and potassium borate.
Secondly, transferred to by mixed liquor in hydrothermal reaction kettle, hydrothermal temperature is 60-160 DEG C, and the reaction time is 1-24h.
Finally, by product respectively with ethanol and deionized water washing, vacuumize 4-24h at 60-120 DEG C.
The invention has the beneficial effects as follows and improve MnO by the doping of boron element
2the surface characteristic of material and microstructure; Doping process is simplified by redox reaction; The controlled MnO of crystal formation, crystal grain and surface topography is prepared fast by hydro thermal method
2.Present invention process is simple, successful, cost are low, efficiency is high.Prepared manganese bioxide material is active and specific capacity is higher, and capacitive property is good, and cyclical stability is high, is a kind of excellent electrode material for super capacitor.
Accompanying drawing explanation
The XRD diffracting spectrum of Fig. 1 electrode prepared by embodiment 1.
The scanning electron microscope (SEM) photograph of Fig. 2 electrode prepared by embodiment 1.
The scanning electron microscope (SEM) photograph of Fig. 3 electrode prepared by embodiment 2.
Fig. 4 is the CV curve chart of electrode when different scanning speed prepared by embodiment 3.
The CV curve chart of Fig. 5 electrode prepared by embodiment 3 and 4, sweep speed 50 mV/s.
Fig. 6 is electrode constant current charge-discharge characteristic curve prepared by embodiment 6.
Embodiment
Explain the present invention further below in conjunction with accompanying drawing and case study on implementation, but scope is not limited only to example.
Embodiment 1
Take potassium permanganate 3.16g, boric acid 12.37g and manganese acetate 1.73g, be dissolved in 20ml respectively, in 10ml and 10ml deionized water, BAS, manganese acetate solution are joined in liquor potassic permanganate successively.Then transfer in hydrothermal reaction kettle by mixed liquor, hydrothermal temperature is 120 DEG C, and the reaction time is 12h.After reaction terminates, by product ethanol and deionized water washing, vacuumize 12h at 80 DEG C.In the process of hydro-thermal reaction, add carbon cloth, boron doped MnO can be made
2be deposited directly on carbon cloth, thus preparation flexible compound electrode of super capacitor.Fig. 1 is this combination electrode XRD collection of illustrative plates, and this manganese oxide material is birnessite-MnO
2.Fig. 2 is the SEM figure of this combination electrode, visible MnO
2three-dimensional network surface texture.
Embodiment 2
Take potassium permanganate 3.16g, boric acid 0.00248g and manganese acetate 1.73g, be dissolved in 20ml respectively, in 10ml and 10ml deionized water, BAS, manganese acetate solution are joined in liquor potassic permanganate successively.Then transfer in hydrothermal reaction kettle by mixed liquor, hydrothermal temperature is 120 DEG C, and the reaction time is 12h.After reaction terminates, by product ethanol and deionized water washing, vacuumize 12h at 80 DEG C.In the process of hydro-thermal reaction, add carbon cloth, boron doped MnO can be made
2be deposited directly on carbon cloth, thus preparation flexible compound electrode of super capacitor.Fig. 3 is the SEM figure of this combination electrode, and with embodiment 1 ratio, the minimizing of boron doping amount obviously can change the depositional mode of manganese dioxide.
Embodiment 3
Take potassium permanganate 3.16g, boric acid 2.48g and manganese nitrate 2.51g, be dissolved in 20ml respectively, in 10ml and 10ml deionized water, BAS, manganese nitrate solution are joined in liquor potassic permanganate successively.Then transfer in hydrothermal reaction kettle by mixed liquor, hydrothermal temperature is 60 DEG C, and the reaction time is 24h.After reaction terminates, by product ethanol and deionized water washing, filter, vacuumize 24h at 60 DEG C.
The ratio of manganese dioxide, carbon black and ptfe emulsion 65:30:5 is in mass ratio mixed, furnishing pulpous state, and be coated in equably in nickel foam, with the tableting under pressure of powder compressing machine at 15MPa, then electrode slice is put into 120 DEG C of vacuum tank vacuumizes 24 hours.Taking saturated calomel electrode as reference electrode, is to electrode with 2 × 2 platinum plate electrodes, and electrolyte is 0.5M Na
2sO
4solution, use China CHI660D in morning electrochemical workstation carries out the cyclic voltammetry of manganese dioxide electrode.Fig. 3 is the cyclic voltammetry curve of electrode under different scanning speed.As can be seen from the figure, the cyclic voltammetry curve of this electrode has good rectangular shape, and the response characteristic of electric current is fine.
Embodiment 4
Take potassium permanganate 3.16g, boric acid 0. 248g and manganese nitrate 2.51g, be dissolved in 20ml respectively, in 10ml and 10ml deionized water, BAS, manganese nitrate solution are joined in liquor potassic permanganate successively.Then transfer in hydrothermal reaction kettle by mixed liquor, hydrothermal temperature is 60 DEG C, and the reaction time is 24h.After reaction terminates, by product ethanol and deionized water washing, filter, vacuumize 24h at 60 DEG C.
The ratio of manganese dioxide, carbon black and ptfe emulsion 65:30:5 is in mass ratio mixed, furnishing pulpous state, and be coated in equably in nickel foam, with the tableting under pressure of powder compressing machine at 15MPa, then electrode slice is put into 120 DEG C of vacuum tank vacuumizes 24 hours.Taking saturated calomel electrode as reference electrode, is to electrode with 2 × 2 platinum plate electrodes, and electrolyte is 0.5M Na
2sO
4solution, use China CHI660D in morning electrochemical workstation carries out the cyclic voltammetry of manganese dioxide electrode.The Cyclic voltamogram curve of Fig. 5 electrode under the sweep speed of 50 mV/s.As can be seen from the figure, the cyclic voltammetry curve of this electrode has good rectangular shape, and the response characteristic of electric current is fine.But compared with embodiment 3, the capacity of material decreases, illustrate that the doping of boron can affect the capacity of manganese dioxide.
Embodiment 5
Take potassium permanganate 7.9g, potassium borate 3.055g and manganese sulfate 1.69g, be dissolved in 20ml respectively, in 10ml and 10ml deionized water, potassium borate solution, manganese sulfate solution are joined in liquor potassic permanganate successively.Then transfer in hydrothermal reaction kettle by mixed liquor, hydrothermal temperature is 160 DEG C, and the reaction time is 1h.After reaction terminates, by product ethanol and deionized water washing, filter, vacuumize 8h at 100 DEG C, prepares boron doped manganese dioxide electrode material for super capacitor.
Embodiment 6
Take potassium permanganate 1.58g, borax 0.7625g and chloric acid manganese 2.52g, be dissolved in 20ml respectively, in 10ml and 10ml deionized water, borax soln, chloric acid manganese solution are joined in liquor potassic permanganate successively.Then transfer in hydrothermal reaction kettle by mixed liquor, hydrothermal temperature is 100 DEG C, and the reaction time is 12h.After reaction terminates, by product ethanol and deionized water washing, filter, vacuumize 4h at 120 DEG C.
The ratio of manganese dioxide, carbon black and ptfe emulsion 65:30:5 is in mass ratio mixed, furnishing pulpous state, and be coated in equably in nickel foam, with the tableting under pressure of powder compressing machine at 15MPa, then electrode slice is put into 120 DEG C of vacuum tank vacuumizes 24 hours.Taking saturated calomel electrode as reference electrode, is to electrode with 2 × 2 platinum plate electrodes, and electrolyte is 0.5M Na
2sO
4solution, use China CHI660D in morning electrochemical workstation carries out the constant current charge-discharge test of manganese dioxide electrode.Fig. 6 is the characteristic working curve of this electrode under different charging and discharging currents pattern.As can be seen from the figure, the charging and discharging curve of this electrode has good symmetry, does not also have the obvious voltage drop caused because of internal resistance during heavy-current discharge.
Claims (4)
1. a preparation method for element-doping manganese bioxide electrode material for super capacitor, is characterized in that the method is specifically:
Borate solution and manganous salt solution are joined successively in liquor potassic permanganate and carry out hydro-thermal reaction, the mol ratio of manganous salt and potassium permanganate is 1:0.5-5; Boron ion concentration is 0.001-5M, and reaction temperature is 60-160 DEG C, and the reaction time is 1-24h, by product respectively with ethanol and deionized water washing, and vacuumize 4-24h at 60-120 DEG C.
2. the preparation method according to right 1, is characterized in that: utilize redox reaction, and doped chemical boron is mixed manganese dioxide lattice.
3. the preparation method according to right 1, is characterized in that: manganous salt comprises manganese sulfate, manganese nitrate, manganese acetate or manganese chloride.
4. the preparation method according to right 1, is characterized in that: borate comprises boric acid, borax or potassium borate.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110277551A (en) * | 2019-06-28 | 2019-09-24 | 陕西科技大学 | One kind is by nonmetallic ion B3+Ion doping MnO2Preparation method |
| CN111410232A (en) * | 2020-04-26 | 2020-07-14 | 张韩生 | Preparation method of manganese dioxide positive electrode material |
| CN111821973A (en) * | 2020-07-21 | 2020-10-27 | 齐鲁工业大学 | Water decomposition hydrogen production photocatalyst and preparation method and application thereof |
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| CN102623188A (en) * | 2012-03-29 | 2012-08-01 | 广东工业大学 | Preparation method for doped manganese oxide octahedral molecular sieve and application thereof |
| CN103258646A (en) * | 2013-04-08 | 2013-08-21 | 杭州电子科技大学 | Preparation method for light flexible electrochemical capacitor electrodes |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111821973B (en) * | 2020-07-21 | 2022-07-15 | 齐鲁工业大学 | Water decomposition hydrogen production photocatalyst and preparation method and application thereof |
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