CN108281293A - A kind of MnO2The preparation method and applications of nano wire - Google Patents
A kind of MnO2The preparation method and applications of nano wire Download PDFInfo
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- CN108281293A CN108281293A CN201810050174.7A CN201810050174A CN108281293A CN 108281293 A CN108281293 A CN 108281293A CN 201810050174 A CN201810050174 A CN 201810050174A CN 108281293 A CN108281293 A CN 108281293A
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- 239000002070 nanowire Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 38
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 26
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 5
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 239000000178 monomer Substances 0.000 claims description 15
- 239000012295 chemical reaction liquid Substances 0.000 claims description 14
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 238000013019 agitation Methods 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- 239000007772 electrode material Substances 0.000 claims description 8
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 7
- 229940012189 methyl orange Drugs 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 3
- -1 Methyl Chemical group 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims 2
- 235000019441 ethanol Nutrition 0.000 claims 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 239000003792 electrolyte Substances 0.000 abstract description 5
- 239000011149 active material Substances 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 239000004744 fabric Substances 0.000 abstract description 2
- 230000014759 maintenance of location Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910003144 α-MnO2 Inorganic materials 0.000 description 2
- 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
- 239000007832 Na2SO4 Substances 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000011565 manganese chloride Substances 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
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The present invention relates to a kind of MnO2The preparation method of nano wire, step are with KMnO4, the concentrated sulfuric acid and homemade polypyrrole be raw material, synthesized MnO relative low temperature (85 DEG C) and short time (1h) are interior2Nano wire.Such preparation method can effectively reduce synthesis cost, need not synthesize MnO in the case of high temperature, high pressure2Nano wire.By the active material MnO of preparation2Nano wire is applied on flexible carbon cloth and is prepared into electrode, in the Na of 1mol/L2SO4By three electrode tests in electrolyte, when current density is 1Ag‑1When specific capacitance a height of 85Fg‑1, while there is fabulous electric conductivity and cyclical stability (current density 5Ag‑198.6%) 1,000 capacitance retention rates of Shi Xunhuan are.
Description
Technical field
The present invention relates to the preparation fields of nano material, and in particular to a kind of MnO2The preparation method of nano wire.
Background technology
Continuing reproducible energy storage method as a kind of, recent ultracapacitor has caused people and greatly closed
Note.Compared to traditional chemical cell, it is capable of providing higher power density, and compared to traditional electrostatic condenser, it has
There is higher energy density.Electrode material is the key factor for determining super capacitor performance quality, generally includes carbonaceous material (stone
Black alkene, carbon nanotube, carbon nano-fiber, carbon clusters etc.), metal oxide/hydroxide (titanium dioxide, manganese dioxide, three oxygen
Change two iron etc.) and conducting polymer (polyaniline (PANI), polypyrrole (PPy) etc.).As one of most important electrode material, gold
Belonging to oxide semiconductor (MOSs) has ideal form and unique structure, they are widely used in each science and technology neck
Domain.Among them, the oxide of manganese, such as MnO2It has been had been a great concern that, since it has the reason of up to 1370F/g
By specific capacitance, at low cost, environmental-friendly, rich reserves, it is considered to be most potential transition metal in next-generation super capacitor
Oxide.
It is well known that MnO2There is a variety of crystal structures, and such as α, β, γ and δ type, they are by the substantially single of regular octahedron
Member [MnO6] be combined by different combinations.In these various MnO2In crystal structure, α-MnO2(2×2
Tunnel structure) best electrode material is seemingly applied in ultracapacitor.Since super capacitor largely depends on
Size or regular octahedron [MnO in tunnel6] interlayer distance.Different tunnel structures has the energy of different transport ions
Power, α-MnO2'sTunnel is by double-strand regular octahedron [MnO6] structure composition, possess sufficient gap and comes
Accommodate ion.Although MnO in theory2Higher specific capacitance and multiplying power property are shown, but among practical application, MnO2Knot
Structure collapses (intercalation/deintercalation of sodium ion in charge/discharge cycle) and active material is unstable (local in charge/discharge cycle
The structural flexibility of dissolving and difference) all limit its development.Although having there is certain methods that can make up these deficiencies,
Cycle performance still needs to further improve in practical application.For example, for short-term loop test, most of loop test result is all
Reduce tens percentage points.With the rapid development of nano material, the electrode material with special nanostructure is easier quilt
People are received, it is the key point of the multiplying power property and repeated charge stability that enhance super capacitor.As far as we know,
Size and the controllable one-dimensional nano structure of crystallinity can provide additional reacting environment for electrochemical reaction, shorten electronics and from
The diffusion path of son, enhances the mechanical performance of electrode.Therefore, be conducive to enhance the various one-dimensional MnO of chemical property2Nano junction
Structure, such as nanorod and nanowire, have been successfully synthesized.
So far, MnO2Nano-material is with MnCl2·4H2O/KMnO4、MnSO4·H2O/KMnO4Solution is original
Material is prepared by hydro-thermal method, but reaction temperature higher (120~150 DEG C), generated time are longer (10~for 24 hours), this is greatly
Increase experimental cost and synthesis difficulty, limit the further genralrlization application of material, therefore develop a kind of simple possible
MnO2The synthetic method of nano wire is very valuable.
Invention content
The object of the present invention is to provide a kind of MnO2The preparation method of nano wire, includes the following steps：
1) by H2SO4、KMnO4It is added in deionized water with polypyrrole, it is fully dispersed, form uniform mixed liquor；
2) mixed liquor under conditions of 80~90 DEG C of temperature is kept into 50~70min, MnO is obtained by the reaction2Nano wire.
Preferably, the KMnO4And H2SO4Mass volume ratio be 1：0.33~0.34；The KMnO4With polypyrrole
Mass ratio is 1：0.018~0.101.
Preferably, the polypyrrole is prepared by the following method：By methyl orange and FeCl36H2O is added to deionized water
In, it is fully dispersed uniformly to add pyrrole monomer, 22~26h of reaction is stirred at room temperature, the black precipitate of formation is described
Polypyrrole.
Preferably, the pyrrole monomer and the volume mass of methyl orange ratio are 1：0.89~0.90, pyrrole monomer and
FeCl36H2The volume mass ratio of O is 1：4.35~4.37.
The present invention provides a kind of new MnO2The preparation method of nano wire, with KMnO4, the concentrated sulfuric acid and homemade polypyrrole
For raw material, MnO has been synthesized in relative low temperature (85 DEG C) and short time (1h)2Nano wire.Such preparation method can be effective
Synthesis cost is reduced, MnO need not be synthesized in the case of high temperature, high pressure2Nano wire.
Preferably, the concrete operations of the step 1) are：By KMnO4It is first dissolved in deionized water, forms KMnO4Solution,
Then in the KMnO4H is added in solution2SO4, magnetic agitation is uniform, forms pre-reaction liquid；It then will be dissolved with polypyrrole
Solution is mixed with the pre-reaction liquid, forms uniform mixed liquor.
Preferably, MnO will be obtained by the reaction in the step 2)2Nano wire deionized water and washes of absolute alcohol, then
Sample is dry in 55~65 DEG C of vacuum drying chamber, obtain MnO2Nano wire finished product.
Preferably, the concrete operations for preparing polypyrrole are：By FeCl36H2O is first dissolved in deionized water, forms FeCl3
Solution, then in the FeCl3Methyl orange is added in solution, ultrasonic disperse is uniform, forms suspension；Then pyrrole monomer is added
It is added to 20~26h of reaction in above-mentioned suspension, magnetic agitation is constantly carried out during reaction.
Preferably, polypyrrole deionized water obtained by the reaction and washes of absolute alcohol is multiple, until filtrate becomes nothing
Color is neutral, finally dry in 45~55 DEG C of vacuum drying oven, obtains polypyrrole finished product.
As a preferred option, include the following steps：
A, the preparation of polypyrrole
By methyl orange and FeCl36H2O is added in deionized water, fully dispersed uniform, pyrrole monomer is added, in room temperature
Under be stirred to react 20~26h, the black precipitate of formation is the polypyrrole；By polypyrrole deionized water obtained by the reaction and
Washes of absolute alcohol is multiple, finally dry in 45~55 DEG C of vacuum drying oven until filtrate becomes colorless neutrality, obtains polypyrrole
Finished product；The pyrrole monomer and the volume mass of methyl orange ratio are 1：0.89~0.90, pyrrole monomer and FeCl36H2The volume of O
Mass ratio is 1：4.35~4.37；
B、MnO2The preparation method of nano wire, which is characterized in that include the following steps：
1) by KMnO4It is first dissolved in deionized water, forms KMnO4Solution, then in the KMnO4It is added in solution
H2SO4, magnetic agitation is uniform, forms pre-reaction liquid；Then the solution dissolved with polypyrrole is mixed with the pre-reaction liquid, shape
At uniform mixed liquor；The KMnO4And H2SO4Mass volume ratio be 1：0.33~0.34；The KMnO4With polypyrrole
Mass ratio is 1：0.018~0.101；
2) mixed liquor is kept into 60min under conditions of 85 DEG C of temperature, MnO is obtained by the reaction2Nano wire；It will react
To MnO2Nano wire deionized water and washes of absolute alcohol, it is then that sample is dry in 55~65 DEG C of vacuum drying chamber,
Obtain MnO2Nano wire finished product.
The MnO that it is another object of the present invention to protect the method for the invention to be prepared2Nano wire.
The last purpose of the present invention is protection MnO of the present invention2Application of the nano wire in preparing electrode material.
The present invention has the advantages that：
1) the method for the present invention is simple, and reaction condition easily reaches, and can be closed in relative low temperature (85 DEG C) and short time (1h)
At MnO2Nano wire can effectively reduce synthesis cost,
2) by the active material MnO of preparation2Nano wire is applied on flexible carbon cloth and is prepared into electrode, 1mol/L's
Na2SO4By three electrode tests in electrolyte, when current density is 1Ag-1When specific capacitance a height of 85Fg-1, while having fabulous
Electric conductivity and cyclical stability (current density 5Ag-198.6%) 6,000 capacitance retention rates of Shi Xunhuan are.
Description of the drawings
Fig. 1 (a) and (b) are MnO2The SEM of the different amplification of nano wire schemes；
Fig. 2 is the Na in 1mol/L2SO4The MnO tested by three-electrode system in solution2The electricity of nano line electrode
Chemical property figure.(a) difference sweeps MnO under speed2CV (cyclic voltammetry curve) curve of nano wire.(b) MnO under different current densities2
Fully electric (GCD) figure of the constant current of nano wire.(c)MnO2The specific capacitance of nano wire and the relational graph of current density.(d)MnO2Nanometer
The impedance spectrum (EIS) of line electrode.(e) it is 5Ag in current density-1When MnO2The cycle life figure of nano line electrode.
Specific implementation mode
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..
Embodiment 1
The present embodiment is related to a kind of MnO2The preparation method of nano wire, includes the following steps：
The preparation of polypyrrole：
0.294g methyl oranges (MO) are dissolved in 180 milliliters of FeCl36H2It in O (1.44g) solution, then stirs, ultrasound
It is uniformly dispersed.330 μ L pyrrole monomers are added in above-mentioned aaerosol solution again, for 24 hours, reaction forms black magnetic agitation at room temperature
Color precipitates.The black precipitate deionized water and washes of absolute alcohol is multiple, until filtrate becomes colorless neutrality, last 50
DEG C vacuum drying oven in dry 12h, obtain PPy (polypyrrole).
MnO2The preparation of nano wire：
1) by 0.265mlH2SO4It is added to 30mlKMnO4It is uniform by magnetic agitation in (0.79g) solution.Then, will
Above-mentioned mixed solution is added in the aqueous solution (20mL) dissolved with 120 milligrams of polypyrrole powder, forms pre-reaction liquid；
2) the pre-reaction liquid is placed in 85 DEG C of water-bath.In this step, reaction time control was at 60 minutes.It will
The sample of synthesis, with deionized water and washes of absolute alcohol, final sample drying in 40 DEG C of vacuum drying chamber for 24 hours, obtains
MnO2Nano wire.
Fig. 1 (a) and (b) are MnO2The SEM of the different amplification of nano wire schemes；Fig. 1 (a) shows MnO2Nano wire is uniform
Distribution, connects each other, crosses each other to form the network-like structure with a large amount of gaps.As Fig. 2 b show that the length of nano wire is several
Micron, diameter is about 30nm, and surface is smooth, without serious agglomeration.
Fig. 2 is the Na in 1mol/L2SO4The MnO tested by three-electrode system in solution2The electrochemistry of nano wire
Property figure.Fig. 2 (a) is MnO2Nano line electrode is in 5-300mVs-1Cyclic voltammetry curve under sweep speed, cyclic voltammetry curve
It is approximately rectangle, shows that sample has ideal capacitive property.With the increase of sweep speed, the face of CV curves institute enclosing region
Product and redox current are consequently increased.Curve, to also not occurring redox peaks between 1V, shows the electrification of material 0
It learns capacitive property and is mainly due to MnO2Faraday's redox reaction and electrode material high reversible.Fig. 2 (b) is electricity
Pole (1Ag under different current densities-1-20Ag-1) constant current discharge figure (GCD figures), curve have height it is linear and symmetrical
Property, show the good invertibity of material and charge-discharge performance.As current density increases, the charging time continuously decreases.It is all
Charging and discharging curve curve feature all triangular in shape, show material capacitive character with relative ideal in neutral electrolyte
Energy.MnO2Specific capacitance and the relation curve of current density calculated using formula C=I Δ t/ (Δ Vm) according to charging and discharging curve
Come, be drawn in Fig. 2 (c), wherein I and t indicate that electric current and the time of constant current discharge, m indicate the matter of electroactive material respectively
Amount, Δ V indicate discharge voltage.MnO2The specific capacitance value of electrode is 85Fg-1It is 1Ag in current density-1When.Fig. 2 (d) MnO2Nanometer
The ac impedance spectroscopy of line electrode, in low frequency range MnO2The straight line angle of gradient of electrode is larger (80 ° of ≈), discloses anti-in redox
Small diffusional resistance (the R of electrolyte ion during answeringW).In addition, MnO2Electrode charge transmission resistance (Rct) is relatively low, shows charge and discharge
Its rapid electric charge shifts in the process.In addition, calculating body resistance (ion resistance, the base of electrolyte of electro-chemical systems
The intrinsic resistance at bottom, the contact resistance of active material and collector) (bulksolutionresistance, that is, Rs) be 1.97 Ω.
The analysis structure of electrochemical impedance spectroscopy (EIS) also further confirm in this nano-electrode material have good kinetics and
Interior resistance.It is 5Ag that current density, which is shown, in Fig. 2 (e)-1, voltage be 0~1V when, the cyclical stability of specimen material.By
After 1000 cycles, the capacitance of sample has slight decline, remains original 98.6%.Illustration is MnO2Nano line electrode exists
Comparison diagram of first five time and last five constant current sides of filling electricity during recycling 1000 times.
Embodiment 2
The present embodiment is related to a kind of MnO2The preparation method of nano wire, includes the following steps：
1) by 0.265mlH2SO4It is added to 30mlKMnO4It is uniform by magnetic agitation in (0.79g) solution.Then, will
Above-mentioned mixed solution is added in the aqueous solution (20mL) dissolved with 80 milligrams of polypyrrole powder, forms pre-reaction liquid；
2) the pre-reaction liquid is placed in 80 DEG C of water-bath.In this step, reaction time control was at 60 minutes.It will
The sample of synthesis, with deionized water and washes of absolute alcohol, final sample dry 12h in 60 DEG C of vacuum drying chamber is obtained
MnO2Nano wire.
Embodiment 3
The present embodiment is related to a kind of MnO2The preparation method of nano wire, includes the following steps：
1) by 0.265mlH2SO4It is added to 30mlKMnO4It is uniform by magnetic agitation in (0.79g) solution.Then, will
Above-mentioned mixed solution is added in the aqueous solution (20mL) dissolved with 140 milligrams of polypyrrole powder, forms pre-reaction liquid；
2) the pre-reaction liquid is placed in 85 DEG C of water-bath.In this step, reaction time control was at 60 minutes.It will
The sample of synthesis, with deionized water and washes of absolute alcohol, final sample dry 12h in 60 DEG C of vacuum drying chamber is obtained
MnO2Nano wire.
Although above having used general explanation, specific implementation mode and experiment, the present invention is made to retouch in detail
It states, but on the basis of the present invention, it can be made some modifications or improvements, this is apparent to those skilled in the art
's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed
Range.
Claims (10)
1. a kind of MnO2The preparation method of nano wire, which is characterized in that include the following steps：
1) by H2SO4、KMnO4It is added in deionized water with polypyrrole, it is fully dispersed, form uniform mixed liquor；
2) mixed liquor under conditions of 80~90 DEG C of temperature is kept into 50~70min, MnO is obtained by the reaction2Nano wire.
2. according to the method described in claim 1, it is characterized in that, the KMnO4And H2SO4Mass volume ratio be 1：0.33
~0.34；The KMnO4Mass ratio with polypyrrole is 1：0.018~0.101.
3. method according to claim 1 or 2, which is characterized in that the polypyrrole is prepared by the following method：By first
Base orange and FeCl36H2O is added in deionized water, fully dispersed uniform, adds pyrrole monomer, reaction 20 is stirred at room temperature
The black precipitate of~26h, formation are the polypyrrole；
Preferably, the pyrrole monomer and the volume mass of methyl orange ratio are 1：0.89~0.90, pyrrole monomer and FeCl36H2O
Volume mass ratio be 1：4.35~4.37.
4. according to claims 1 to 3 any one of them method, which is characterized in that the concrete operations of the step 1) are：It will
KMnO4It is first dissolved in deionized water, forms KMnO4Solution, then in the KMnO4H is added in solution2SO4, magnetic agitation is equal
It is even, form pre-reaction liquid；Then the solution dissolved with polypyrrole is mixed with the pre-reaction liquid, forms uniform mixed liquor.
5. method according to claim 1 or 4, which is characterized in that MnO will be obtained by the reaction in the step 2)2Nano wire is used
Deionized water and washes of absolute alcohol, it is then that sample is dry in 55~65 DEG C of vacuum drying chamber, obtain MnO2Nano wire
Finished product.
6. according to claims 1 to 3 any one of them method, which is characterized in that the concrete operations for preparing polypyrrole are：It will
FeCl36H2O is first dissolved in deionized water, forms FeCl3Solution, then in the FeCl3Methyl orange is added in solution, ultrasound
It is uniformly dispersed, forms suspension；Then pyrrole monomer is added to 20~26h of reaction in above-mentioned suspension, during reaction
Constantly carry out magnetic agitation.
7. method according to claim 1 or 6, which is characterized in that by polypyrrole deionized water obtained by the reaction and nothing
Water-ethanol cleaning is multiple, finally dry in 45~55 DEG C of vacuum drying oven until filtrate becomes colorless neutrality, obtain polypyrrole at
Product.
8. according to claim 1~7 any one of them method, which is characterized in that include the following steps：
A, the preparation of polypyrrole
By methyl orange and FeCl36H2O is added in deionized water, fully dispersed uniform, adds pyrrole monomer, stirs at room temperature
20~26h of reaction is mixed, the black precipitate of formation is the polypyrrole；By polypyrrole deionized water obtained by the reaction and anhydrous
Ethyl alcohol cleaning is multiple, finally dry in 45~55 DEG C of vacuum drying oven until filtrate becomes colorless neutrality, obtain polypyrrole at
Product；The pyrrole monomer and the volume mass of methyl orange ratio are 1：0.89~0.90, pyrrole monomer and FeCl36H2The volume matter of O
Amount is than being 1：4.35~4.37；
B、MnO2The preparation method of nano wire, which is characterized in that include the following steps：
1) by KMnO4It is first dissolved in deionized water, forms KMnO4Solution, then in the KMnO4H is added in solution2SO4, magnetic
Power stirs evenly, and forms pre-reaction liquid；Then the solution dissolved with polypyrrole is mixed with the pre-reaction liquid, is formed uniform
Mixed liquor；The KMnO4And H2SO4Mass volume ratio be 1：0.33~0.34；The KMnO4Mass ratio with polypyrrole is
1：0.018~0.101；
2) mixed liquor is kept into 60min under conditions of 85 DEG C of temperature, MnO is obtained by the reaction2Nano wire；It will be obtained by the reaction
MnO2Nano wire deionized water and washes of absolute alcohol, it is then that sample is dry in 55~65 DEG C of vacuum drying chamber, it obtains
To MnO2Nano wire finished product.
9. the MnO that any one of claim 1~8 the method is prepared2Nano wire.
10. the MnO described in claim 92Application of the nano wire in preparing electrode material.
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