CN102154701B - Method for preparing manganese molybdate/cobalt molybdate hierarchical heterostructure nanowires - Google Patents
Method for preparing manganese molybdate/cobalt molybdate hierarchical heterostructure nanowires Download PDFInfo
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- 239000011572 manganese Substances 0.000 title claims abstract description 95
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 title claims abstract description 95
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 94
- KYYSIVCCYWZZLR-UHFFFAOYSA-N cobalt(2+);dioxido(dioxo)molybdenum Chemical compound [Co+2].[O-][Mo]([O-])(=O)=O KYYSIVCCYWZZLR-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000002070 nanowire Substances 0.000 title claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 33
- 238000010992 reflux Methods 0.000 claims abstract description 25
- 239000000243 solution Substances 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 22
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003990 capacitor Substances 0.000 claims abstract description 14
- 239000002073 nanorod Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 9
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims abstract description 8
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000000593 microemulsion method Methods 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 238000002360 preparation method Methods 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 11
- 206010013786 Dry skin Diseases 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000003760 magnetic stirring Methods 0.000 claims description 7
- 239000007772 electrode material Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 abstract description 7
- 239000011149 active material Substances 0.000 abstract description 4
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 abstract 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 abstract 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 abstract 1
- 229910004619 Na2MoO4 Inorganic materials 0.000 abstract 1
- 229910018890 NaMoO4 Inorganic materials 0.000 abstract 1
- 238000004140 cleaning Methods 0.000 abstract 1
- 239000012153 distilled water Substances 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000011565 manganese chloride Substances 0.000 abstract 1
- 235000002867 manganese chloride Nutrition 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 235000015393 sodium molybdate Nutrition 0.000 abstract 1
- 239000011684 sodium molybdate Substances 0.000 abstract 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 abstract 1
- 238000001069 Raman spectroscopy Methods 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a method for preparing manganese molybdate/cobalt molybdate hierarchical heterostructure nanowires. The method comprises the following steps of: preparing a NaMoO4 aqueous solution and a MnCl2aqueous solution; proportioning in a certain ratio of the NaMoO4aqueous solution to the MnCl2 aqueous solution to CTAB (Cetyltrimethyl Ammonium Bromide) to n-butyl alcohol to isooctane and preparing manganese molybdate nanorods by using a microemulsion method; adding the manganese molybdate nanorods into distilled water, stirring and ultrasonically cleaning to obtain transparent liquid; and adding the liquid into a flask, placing the flask in an oil bath of between 60 and 80 DEG C, condensing and refluxing, adding a CoCl2 solution and a Na2MoO4 solution with different concentrations in turn every certain time, stirring to react so as to obtain a product, separating and drying the product to obtain the manganese molybdate/cobalt molybdate hierarchical heterostructure nanowires, wherein the lengths of the nanowires reach 10 microns and the diameters of the nanowires are between 500 and 1,000nm; the manganese molybdate nanorods in the hierarchical heterostructure nanowires are used as a main material and the diameters of the manganese molybdate nanorods are between 300 and 500; and the cobalt molybdate is branch nanorods which orderly grow on the surfaces of the manganese molybdate nanorods and the diameters of the cobalt molybdate nanorods are between 30 and 50nm. The material has excellent electrochemical performance and can be used as an active material for electrodes of electrochemical super capacitors. The method has the advantages of low-cost raw materials, simple process and environmental friendliness.
Description
Technical field
The invention belongs to nano material and electrochemical device technical field, be specifically related to the preparation method of a kind of manganese molybdate/cobalt molybdate classification heterogeneous structural nano line, this material can be used as the electric chemical super capacitor electrode active material.
Background technology
Electric chemical super capacitor is a kind of novel energy-storing equipment and device between storage battery and conventional capacitor, and it has the specific capacitance bigger than conventional capacitor, than the bigger specific power of storage battery with recycle the life-span.Utilize ultracapacitor and battery to form hybrid power system, can satisfy the needs of high power density output occasions such as electric automobile startup, acceleration well.It can be applied to a lot of fields, as: hybrid-electric car, fuel cell, mobile phone, computer etc.At present, most of under normal conditions commercial ultracapacitors are to be processed by the material with carbon element of high-specific surface area, and in the aqueous solution or organic bath electrolyte, it reaches 4F/g than electric capacity.Yet these ultracapacitors are because its lower specific capacitance can't provide enough energy and power densities.In addition, its specific capacitance will descend rapidly because ultracapacitor is worked under high current density, so can only under low current density, work, this has also limited its application.Therefore, through increasing its specific area and attempting the complex heterogeneous structure to improve its specific capacitance and to be implemented in that work has become the research focus under the high current density.
The heterogeneous nano material of classification is because architectural features such as its big specific area, better permeability, more surface activity position possess in many-sided application prospects such as optics, catalysis, electrochemistry it.As molybdate, cobalt molybdate and manganese molybdate all possess good electrochemical, in the application of electrochemical energy storing device such as lithium battery, have bright prospects.
In addition, adopt the method for simple condensing reflux, in not containing any surfactant and aqueous organic, can realize the synthetic of product at normal temperatures and pressures and construct, meet the requirement of Green Chemistry.Simultaneously, only need controlling reaction time and reaction temperature, can realize the product controlledly synthesis, method is simple, is beneficial to the marketization and promotes.
Summary of the invention
The object of the present invention is to provide that a kind of technology is simple, the requirement that meets Green Chemistry, have the preparation method of the manganese molybdate/cobalt molybdate classification heterogeneous structural nano line of good electric chemical property.
To achieve these goals, technical scheme of the present invention is:
A kind of electric chemical super capacitor electrode active material is characterized in that: this material is manganese molybdate/cobalt molybdate classification heterogeneous structural nano line, and nanowire length reaches 10 microns; Diameter is 500～1000nm, and the manganese molybdate nanometer rods is the trunk material in the classification heterogeneous structural nano line, and diameter is 300～500nm; Cobalt molybdate is a nanometer rods; It is orderly is grown in the manganese molybdate nanorod surfaces, and diameter is 30～50nm, about 1: 1 of manganese molybdate and cobalt molybdate mol ratio.
Annotate: symbol "/" is represented a kind of heterostructure in manganese molybdate/cobalt molybdate classification heterogeneous structural nano line.
The preparation method of a kind of manganese molybdate of the present invention/cobalt molybdate classification heterogeneous structural nano line comprises the steps:
1) preparation 0.5mol/L NaMoO
4The aqueous solution and 0.5mol/L MnCl
2The aqueous solution is pressed the NaMoO that is prepared
4The aqueous solution: MnCl
2The ratio batching of the aqueous solution: softex kw: n-butanol: isooctane=1.39ml: 1.39ml: 1.56g: 1.6ml: 9ml; Join in the reactor, utilize microemulsion method, used magnetic stirrer 1～2 hour; Ageing 12 hours; Utilize ethanol centrifuge washing repeatedly, prepare the manganese molybdate nanometer rods, subsequent use;
2) the manganese molybdate nanometer rods that step 1) is obtained is as the trunk material; The manganese molybdate nanometer rods of 0.2mmol is joined in the 40ml deionized water; With stirring under the magnetic stirring apparatus room temperature 10～15 minutes; Place ultrasonic cleaner with the frequency sonicated of 40Hz 0.2 hour then, obtain transparency liquid, subsequent use;
3) with step 2) obtain placing 60～80 ℃ oil bath in the liquid immigration there-necked flask, adopt the condensing reflux method, whenever added the CoCl that 1ml concentration is respectively 0.08mol/L, 0.06mo/L, 0.04mol/L, 0.02mol/L respectively successively at a distance from 1 hour
2Solution and Na
2MoO
4Solution accompanies by magnetic agitation, reacts 3.5～5 hours, obtains the condensing reflux product;
4) it is 1: 1 liquid repeatedly behind the centrifuge washing that the condensing reflux product that step 3) is obtained uses ethanol and deionized water volume ratio, filtration;
5) product that step 4) is filtered promptly obtains manganese molybdate/cobalt molybdate classification heterogeneous structural nano line products 80 ℃ of dryings 12～24 hours.
Manganese molybdate/cobalt molybdate classification heterogeneous structural nano the line of the present invention's preparation is as Asymmetric Electric chemistry electrode of super capacitor active material; All the other steps of the preparation method of asymmetric electric chemical super capacitor are identical with common preparation method; Work electrode consists of the 60wt% active material, the conductive agent of 35.5wt% (acetylene black), and 4.5wt% binding agent (polytetrafluoroethylene); Electrolyte is the 2M NaOH aqueous solution, adopts under the three-electrode method room temperature and tests.
The invention has the beneficial effects as follows: adopt the method for condensing reflux to prepare manganese molybdate/cobalt molybdate classification heterogeneous structural nano line, this material can be implemented under the high current density and use as the electric chemical super capacitor electrode active material, has high specific capacitance.Technology of the present invention is simple, in not containing any surfactant and aqueous organic, can realize the synthetic of product at normal temperatures and pressures and construct, and has reduced energy consumption and production cost, meets the requirement of Green Chemistry.Simultaneously, only need controlling reaction time and reaction temperature, can realize the product controlledly synthesis, method is simple, is beneficial to the marketization and promotes.
Manganese molybdate among the present invention/cobalt molybdate classification heterogeneous structural nano line is confirmed by x-ray diffractometer.X-ray diffracting spectrum shows (referring to Fig. 1), and there is MnMoO in the manganese molybdate/cobalt molybdate classification heterogeneous structural nano line that obtains through condensing reflux
4, Mn
15Mo
8O
11, CoMoO
4Three kinds of phases, field emission scanning electron microscope test shows (referring to Fig. 3), product manganese molybdate/cobalt molybdate classification heterogeneous structural nano linear diameter is the about 10 μ m of 500～1000nm, length.The chemical bond of this product can be confirmed that the stronger key that Raman figure (referring to Fig. 2) shows manganese molybdate/cobalt molybdate classification heterogeneous structural nano line is mainly at 200～1200cm by Raman spectrum analysis
-1The raman frequency scope in can be observed, only be positioned at 872cm
-1The peak at place can not be corresponding with (b) cobalt molybdate and peak in (c) manganese molybdate, and this maybe be owing to having formed new Co-Mn-Mo key.The details of manganese molybdate/cobalt molybdate classification heterogeneous structural nano line can be obtained by transmission electron microscope picture (referring to Fig. 4, Fig. 5); Can observe the nanometer rods diameter 30～50nm of cobalt molybdate branch; The cobalt molybdate branch nanometer rods at close-ups node place; Show that it is not the loose manganese molybdate trunk material surface that is attached to that cobalt molybdate nano props up rod, but the manganese molybdate inside of growing into.High-resolution-ration transmission electric-lens shows that the interlamellar spacing of manganese molybdate and cobalt molybdate is respectively 0.288nm and 0.335nm.Power spectrum (EDS is referring to Fig. 6)) shows; A nanometer rods of classification heterogeneous structural nano line is made up of three kinds of elements of Co Mo O; And classification heterogeneous structural nano line integral body is made up of four kinds of elements of Co Mo Mn O; Shown the nanometer that is grown in the surface prop up rod mainly be cobalt molybdate and classification heterogeneous structural nano line whole be the mixture of manganese molybdate and cobalt molybdate, the analysis result of this and XRD is on all four.
The electric chemical super capacitor of manganese molybdate among the present invention/cobalt molybdate classification heterogeneous structural nano line adopts three-electrode method; The composition of work electrode: 60wt% active material (manganese molybdate/cobalt molybdate classification heterogeneous structural nano line); (acetylene black) of conductive agent 35.5wt%, and 4.5wt% binding agent (polytetrafluoroethylene), platinum electrode and calomel electrode are used separately as electrode and reference electrode; Electrolyte is the NaOH aqueous solution of 2M, and test is at room temperature carried out.
Manganese molybdate/cobalt molybdate classification heterogeneous structural nano line electrode can reach 204.1F/g than electric capacity and energy density, 170.1F/g and 28.4Wh/kg, 23.6Wh/kg when current density is 0.5A/g and 1A/g.The capacitive property of manganese molybdate/cobalt molybdate classification heterogeneous structural nano line is far above the performance of simple manganese molybdate and cobalt molybdate nano rod.Along with the increase of current density, descend than electric capacity and energy density, this is mainly due to forming SEI film (one deck is covered in the passivation layer of electrode material surface).Still is initial 73% (referring to Fig. 8, Fig. 9) than electric capacity through 1000 circulation backs than electric capacity.
Manganese molybdate/cobalt molybdate classification heterostructure is in close relations to influence and its specific area of capacity, and the specific area of manganese molybdate nanometer rods trunk material is 3.17m
2/ g, the manganese molybdate/cobalt molybdate classification heterogeneous structural nano line specific area after process is constructed is up to 54.06m
2/ g is than the manganese molybdate nanometer rods (15m that has smaller szie that reports in the document
2/ g) and cobalt molybdate nano rod (25m
2/ g) taller, so interior active point can contact with electrode more fully.In addition, because its special hierarchy has significantly reduced the generation of self aggregation phenomenon.The 3rd, compare with simple cobalt molybdate nano rod, be grown in the order that cobalt molybdate nano rod on the trunk material manganese molybdate has height, the redox reaction that this structure can be the surface provides more active sites, also makes Na
+Embedding with deviate to be more prone to, these three factors are to improve the key of ultracapacitor specific capacity.This shows that the classification heterostructure can improve chemical property effectively, and manganese molybdate/cobalt molybdate classification heterogeneous structural nano line is a kind of electric chemical super capacitor material that development potentiality is arranged very much.
Description of drawings
Fig. 1 is the XRD figure of manganese molybdate/cobalt molybdate classification heterogeneous structural nano line of embodiment 1 trunk material manganese molybdate nanometer rods required with preparing product
Among the figure: (a) being the XRD figure of simple trunk material manganese molybdate nanometer rods, (b) is the XRD figure of manganese molybdate/cobalt molybdate classification heterogeneous structural nano line.
Fig. 2 is the manganese molybdate/cobalt molybdate classification heterogeneous structural nano line of embodiment 1 and the Raman figure of corresponding manganese molybdate nanometer rods and cobalt molybdate nano rod
Among the figure: (a) being the Raman figure of manganese molybdate/cobalt molybdate classification heterogeneous structural nano line, (b) is the Raman figure of cobalt molybdate, (c) is the Raman figure of manganese molybdate.
Fig. 3 is the FESEM figure of manganese molybdate/cobalt molybdate classification heterogeneous structural nano line of embodiment 1
Fig. 4 is the TEM figure at manganese molybdate/cobalt molybdate classification heterogeneous structural nano line heterojunction node place of embodiment 1
Fig. 5 is the HRTEM figure at manganese molybdate/cobalt molybdate classification heterogeneous structural nano line heterojunction node place of embodiment 1
Fig. 6 is the EDS figure of manganese molybdate/cobalt molybdate classification heterogeneous structural nano line of embodiment 1
Among the figure: (a) institute's favored area is that the nanometer rods part is propped up by the branch of classification heterogeneous structural nano line, and institute's favored area (b) is that the classification heterostructure is whole.
Fig. 7 is the synthesis mechanism figure of manganese molybdate/cobalt molybdate classification heterogeneous structural nano line of embodiment 1
Fig. 8 is that manganese molybdate/cobalt molybdate classification heterogeneous structural nano line of embodiment 1 is the charging and discharging curve figure of electrode of super capacitor
Fig. 9 be manganese molybdate/cobalt molybdate classification heterogeneous structural nano line of embodiment 1 be the first charge-discharge of electrode of super capacitor bent and 1000 times after charging and discharging curve figure.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to following embodiment.
Embodiment 1:
The preparation method of manganese molybdate/cobalt molybdate classification heterogeneous structural nano line, it comprises the steps:
1) preparation 0.5mol/L NaMoO
4The aqueous solution and 0.5mol/L MnCl
2The aqueous solution is by the NaMoO for preparing
4The aqueous solution: MnCl
2The aqueous solution: CTAB (softex kw): the ratio batching of n-butanol: isooctane=1.39ml: 1.39ml: 1.56g: 1.6ml: 9ml, join in the reactor, utilize microemulsion method; Used magnetic stirrer 1 hour; Ageing 12 hours utilizes ethanol centrifuge washing repeatedly, prepares the manganese molybdate nanometer rods; About 10 microns of diameter 300～500nm, length, subsequent use;
2) the manganese molybdate nanometer rods that step 1) is obtained is as the trunk material; The manganese molybdate nanometer rods of 0.2mmol is joined in the 40ml deionized water; With stirring 10 minutes under the magnetic stirring apparatus room temperature; Place ultrasonic cleaner with the frequency sonicated of 40Hz 0.2 hour then, obtain nearly colourless transparent liquid, subsequent use;
3) with step 2) obtain liquid and move in the there-necked flask, place in the middle of 60 ℃ the oil bath, adopt the condensing reflux method, whenever added the CoCl that 1ml concentration is respectively 0.08mol/L, 0.06mo/L, 0.04mol/L, 0.02mol/L respectively successively at a distance from 1 hour
2Solution and Na
2MoO
4Solution accompanies by slight magnetic agitation, reacts 4 hours, obtains the condensing reflux product;
4) the condensing reflux product that step 3) is obtained is used ethanol: the liquid of deionized water=1: 1 is centrifuge washing repeatedly;
5) product with the step 4) filtration washing obtained manganese molybdate/cobalt molybdate classification heterogeneous structural nano line products in 12 hours 80 ℃ of dryings.
Embodiment 2:
The preparation method of manganese molybdate/cobalt molybdate classification heterogeneous structural nano line, it comprises the steps:
1) preparation 0.5mol/L NaMoO
4The aqueous solution and 0.5mol/L MnCl
2The aqueous solution is by the NaMoO for preparing
4The aqueous solution: MnCl
2The ratio batching of the aqueous solution: CTAB: n-butanol: isooctane=1.39ml: 1.39ml: 1.56g: 1.6ml: 9ml joins in the reactor, utilizes microemulsion method; Used magnetic stirrer 2 hours; Ageing 12 hours utilizes ethanol centrifuge washing repeatedly, prepares the manganese molybdate nanometer rods; About 10 microns of diameter 300～500nm, length, subsequent use;
2) the manganese molybdate nanometer rods that step 1) is obtained is as the trunk material; The manganese molybdate nanometer rods of 0.2mmol is joined in the 40ml deionized water; With stirring 15 minutes under the magnetic stirring apparatus room temperature; Place ultrasonic cleaner with the frequency sonicated of 40Hz 0.2 hour then, obtain nearly colourless transparent liquid, subsequent use;
3) with step 2) obtain liquid and move in the there-necked flask, place in the middle of 65 ℃ the oil bath, adopt the condensing reflux method, whenever added the CoCl that 1ml concentration is respectively 0.08mol/L, 0.06mo/L, 0.04mol/L, 0.02mol/L respectively successively at a distance from 1 hour
2Solution and Na
2MoO
4Solution accompanies by slight magnetic agitation, reacts 5 hours, obtains the condensing reflux product;
4) the condensing reflux product that step 3) is obtained is used ethanol: the liquid of deionized water=1: 1 is centrifuge washing repeatedly;
5) product with the step 4) filtration washing obtained manganese molybdate/cobalt molybdate classification heterogeneous structural nano line products in 24 hours 80 ℃ of dryings.
Embodiment 3:
The preparation method of manganese molybdate/cobalt molybdate classification heterogeneous structural nano line, it comprises the steps:
1) preparation 0.5mol/L NaMoO
4The aqueous solution and 0.5mol/L MnCl
2The aqueous solution is by the NaMoO for preparing
4The aqueous solution: MnCl
2The ratio batching of the aqueous solution: CTAB: n-butanol: isooctane=1.39ml: 1.39ml: 1.56g: 1.6ml: 9ml joins in the reactor, utilizes microemulsion method; Used magnetic stirrer 1 hour; Ageing 12 hours utilizes ethanol centrifuge washing repeatedly, prepares the manganese molybdate nanometer rods; About 10 microns of diameter 300～500nm, length, subsequent use;
2) the manganese molybdate nanometer rods that step 1) is obtained is as the trunk material; The manganese molybdate nanometer rods of 0.2mmol is joined in the 40ml deionized water; With stirring 10 minutes under the magnetic stirring apparatus room temperature; Place ultrasonic cleaner with the frequency sonicated of 50Hz 0.2 hour then, obtain nearly colourless transparent liquid, subsequent use;
3) with step 2) obtain liquid and move in the there-necked flask, place in the middle of 80 ℃ the oil bath, adopt the condensing reflux method, whenever added the CoCl that 1ml concentration is respectively 0.08mol/L, 0.06mo/L, 0.04mol/L, 0.02mol/L respectively successively at a distance from 1 hour
2Solution and Na
2MoO
4Solution accompanies by slight magnetic agitation, reacts 3 hours, obtains the condensing reflux product;
4) the condensing reflux product that step 3) is obtained is used ethanol: the liquid of deionized water=1: 1 is centrifuge washing repeatedly;
5) product with the step 4) filtration washing obtained manganese molybdate/cobalt molybdate classification heterogeneous structural nano line products in 20 hours 80 ℃ of dryings.
Embodiment 4:
The preparation method of manganese molybdate/cobalt molybdate classification heterogeneous structural nano line, it comprises the steps:
1) preparation 0.5mol/L NaMoO
4The aqueous solution and 0.5mol/L MnCl
2The aqueous solution is by the NaMoO for preparing
4The aqueous solution: MnCl
2The ratio batching of the aqueous solution: CTAB: n-butanol: isooctane=1.39ml: 1.39ml: 1.56g: 1.6ml: 9ml joins in the reactor, utilizes microemulsion method; Used magnetic stirrer 1.5 hours; Ageing 12 hours utilizes ethanol centrifuge washing repeatedly, prepares the manganese molybdate nanometer rods; About 10 microns of diameter 300～500nm, length, subsequent use;
2) the manganese molybdate nanometer rods that step 1) is obtained is as the trunk material; The manganese molybdate nanometer rods of 0.2mmol is joined in the 50ml deionized water; With stirring 12 minutes under the magnetic stirring apparatus room temperature; Place ultrasonic cleaner with the frequency sonicated of 40Hz 0.2 hour then, obtain nearly colourless transparent liquid, subsequent use;
3) with step 2) obtain liquid and move in the there-necked flask, place in the middle of 60 ℃ the oil bath, adopt the condensing reflux method, whenever added the CoCl that 1ml concentration is respectively 0.08mol/L, 0.06mo/L, 0.04mol/L, 0.02mol/L respectively successively at a distance from 1 hour
2Solution and Na
2MoO
4Solution accompanies by slight magnetic agitation, reacts 5 hours, obtains the condensing reflux product;
4) the condensing reflux product that step 3) is obtained is used ethanol: the liquid of deionized water=1: 1 is centrifuge washing repeatedly;
5) product with the step 4) filtration washing obtained manganese molybdate/cobalt molybdate classification heterogeneous structural nano line products in 12 hours 80 ℃ of dryings.
Embodiment 5:
The preparation method of manganese molybdate/cobalt molybdate classification heterogeneous structural nano line, it comprises the steps:
1) preparation 0.5mol/L NaMoO
4The aqueous solution and 0.5mol/L MnCl
2The aqueous solution is by the NaMoO for preparing
4The aqueous solution: MnCl
2The ratio batching of the aqueous solution: CTAB: n-butanol: isooctane=1.39ml: 1.39ml: 1.56g: 1.6ml: 9ml joins in the reactor, utilizes microemulsion method; Used magnetic stirrer 1 hour; Ageing 12 hours utilizes ethanol centrifuge washing repeatedly, prepares the manganese molybdate nanometer rods; About 10 microns of diameter 300～500nm, length, subsequent use;
2) the manganese molybdate nanometer rods that step 1) is obtained is as the trunk material; The manganese molybdate nanometer rods of 0.2mmol is joined in the 40ml deionized water; With stirring 15 minutes under the magnetic stirring apparatus room temperature; Place ultrasonic cleaner with the frequency sonicated of 40Hz 0.2 hour then, obtain nearly colourless transparent liquid, subsequent use;
3) with step 2) obtain liquid and move in the there-necked flask, place in the middle of 65 ℃ the oil bath, adopt the condensing reflux method, whenever added the CoCl that 1ml concentration is respectively 0.08mol/L, 0.06mo/L, 0.04mol/L, 0.02mol/L respectively successively at a distance from 1 hour
2Solution and Na
2MoO
4Solution accompanies by slight magnetic agitation, reacts 4 hours, obtains the condensing reflux product;
4) the condensing reflux product that step 3) is obtained is used ethanol: the liquid of deionized water=1: 1 is centrifuge washing repeatedly;
5) product with the step 4) filtration washing obtained manganese molybdate/cobalt molybdate classification heterogeneous structural nano line products in 24 hours 80 ℃ of dryings.
Claims (2)
1. electric chemical super capacitor electrode active material, it is characterized in that: this material is manganese molybdate/cobalt molybdate classification heterogeneous structural nano line, and nanowire length reaches 10 microns; Diameter is 500～1000nm, and the manganese molybdate nanometer rods is the trunk material in the classification heterogeneous structural nano line, and diameter is 300～500nm; Cobalt molybdate is a nanometer rods; It is orderly is grown in the manganese molybdate nanorod surfaces, and diameter is 30～50nm, manganese molybdate and cobalt molybdate mol ratio 1: 1.
2. the preparation method of manganese molybdate/cobalt molybdate classification heterogeneous structural nano line is characterized in that it comprises the steps:
1) preparation 0.5mol/L Na
2MoO
4The aqueous solution and 0.5mol/L MnCl
2The aqueous solution is pressed the Na that is prepared
2MoO
4The aqueous solution: MnCl
2The ratio batching of the aqueous solution: softex kw: n-butanol: isooctane=1.39ml: 1.39ml: 1.56g: 1.6ml: 9ml; Join in the reactor, utilize microemulsion method, used magnetic stirrer 1～2 hour; Ageing 12 hours; Utilize ethanol centrifuge washing repeatedly, prepare the manganese molybdate nanometer rods, subsequent use;
2) the manganese molybdate nanometer rods that step 1) is obtained is as the trunk material; The manganese molybdate nanometer rods of 0.2mmol is joined in the 40ml deionized water; With stirring under the magnetic stirring apparatus room temperature 10～15 minutes; Place ultrasonic cleaner with the frequency sonicated of 40Hz 0.2 hour then, obtain transparency liquid, subsequent use;
3) with step 2) obtain placing 60～80 ℃ oil bath in the liquid immigration there-necked flask, adopt the condensing reflux method, whenever added the CoCl that 1mL concentration is 0.08mol/L respectively successively at a distance from 1 hour
2Solution and 1mL concentration are the Na of 0.0gmol/L
2MoO
4Solution, 1mL concentration are the CoCl of 0.06mol/L
2Solution and 1mL concentration are the Na of 0.06mol/L
2MoO
4Solution, 1mL concentration are the CoCl of 0.04mol/L
2Solution and 1mL concentration are the Na of 0.04mol/L
2MoO
4Solution, 1mL concentration are the CoCl of 0.02mol/L
2Solution and 1mL concentration are the Na of 0.02mol/L
2MoO
4Solution accompanies by magnetic agitation, continues reaction 3.5～5 hours, obtains the condensing reflux product;
4) it is 1: 1 liquid repeatedly behind the centrifuge washing that the condensing reflux product that step 3) is obtained uses ethanol and deionized water volume ratio, filtration;
5) product that step 4) is filtered promptly obtains manganese molybdate/cobalt molybdate classification heterogeneous structural nano line products 80 ℃ of dryings 12～24 hours.
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| CN102502885B (en) * | 2011-11-07 | 2013-12-11 | 河北联合大学 | Method for preparing cobalt molybdate material in which micron rod is assembled by nano sheets |
| CN102502846B (en) * | 2011-11-07 | 2013-12-11 | 河北联合大学 | Manganese molybdate material having micron rod structure assembled by nano sheets |
| CN102502847B (en) * | 2011-11-07 | 2013-12-11 | 河北联合大学 | Preparation method for manganese molybdate nanospheres regular in shape |
| CN102616857A (en) * | 2012-01-16 | 2012-08-01 | 渤海大学 | Preparation method of manganese molybdate microcrystal |
| CN103811189B (en) * | 2014-02-12 | 2016-08-17 | 东华大学 | A kind of cobalt molybdate and the preparation method of graphene nanocomposite material |
| CN105742598A (en) * | 2016-03-16 | 2016-07-06 | 武汉理工大学 | Graphene clad Fe2(MoO4)3 nanoparticle and preparation method and application thereof |
| CN106887346B (en) * | 2017-03-07 | 2018-04-13 | 信阳师范学院 | The electrostatic spinning preparation method and manganese molybdate porous nanotube of a kind of manganese molybdate porous nanotube |
| CN107032406B (en) * | 2017-05-08 | 2018-09-18 | 陕西科技大学 | A kind of micro-nano beam of manganese molybdate and preparation method thereof |
| CN107459063B (en) * | 2017-07-25 | 2019-10-29 | 陕西科技大学 | A kind of manganese molybdate micro Nano material and its preparation method and application |
| CN108598399B (en) * | 2018-04-10 | 2021-03-23 | 陕西科技大学 | Cobalt oxide/molybdenum oxide hierarchical heterostructure nanosheet and preparation method thereof |
| CN109935475A (en) * | 2019-03-19 | 2019-06-25 | 河北科技大学 | The synthetic method of cobalt molybdate for electrode material for super capacitor |
| CN114249544B (en) * | 2022-03-01 | 2022-05-20 | 青岛理工大学 | Z-type heterojunction composite photo-anode membrane, one-step hydrothermal preparation method and application thereof |
| CN115084485B (en) * | 2022-07-29 | 2023-08-18 | 大气(广东)科技发展有限公司 | Carbon fiber loaded manganese molybdate/manganese oxide nano heterojunction material and preparation method and application thereof |
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