CN104876277B - A kind of manganese vanadate nano material and its synthetic method, application - Google Patents
A kind of manganese vanadate nano material and its synthetic method, application Download PDFInfo
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Abstract
The invention discloses a kind of manganese vanadate nano material and its synthetic method, application, belong to field of inorganic nonmetallic material.Using one step hydro thermal method, by regulating and controlling reaction condition so that manganese, vanadium, oxygen mix on a molecular scale, prepare MnV12O31·10H2O nano wire, has expanded the species of manganese vanadate nano material；Further with " dipping dry " method by conducting polymer Polyglycolic acid fibre polystyrolsulfon acid（PEDOT‑PSS）It is coated on MnV12O31·10H2O nano wire top layer obtains modified nano material MnV of complex12O31·10H2O/PEDOT PSS, and by MnV12O31·10H2O nano wire and nano material MnV of complex modification12O31·10H2O/PEDOT PSS is applied to the positive electrode of lithium ion battery.Present invention has the advantages that not requiring the use of any surfactant or organic formwork, environmental friendliness, products pure in building-up process；Material morphology size uniformity；Synthetic method craft is simple, condition is controlled, suitable batch produces, and is that applied research establishes good basis.
Description
Technical field
The invention belongs to field of inorganic nonmetallic material is and in particular to a kind of manganese vanadate nano material and its synthetic method and should
With.
Background technology
Manganese vanadate is a kind of important inorganic material, according to manganese, vanadium, oxygen ratio difference, manganese vanadate has multiple differences
Composition and structure.Such material due to having good electricity, optics and electrochemical properties, in electricity device, optics
And lithium ion battery aspect has good application prospect.The synthetic method of traditional manganese vanadate is mainly high temperature solid state reaction,
The manganese vanadate powder of random pattern can be prepared by high temperature solid-state method, this course of reaction consumption can be very high, and the cycle
Longer, product is usually block materials, and size is larger and uneven.In recent years, with the continuous development of nanotechnology, Ren Menfa
Existing nano material, due to its unique microstructure, is demonstrated by more excellent performance in a lot of fields, therefore all kinds of nanometer materials
The research of the preparation technology of material and correlated performance has been increasingly becoming study hotspot.Patent No. 201310074998.5, entitled
The patent of " a kind of Manganese vanadate nanoneedle structure and its synthetic method " provides one kind and consists of MnV2O5The needle-like of iris phase
Structure；Application No. 201410400470.7, the patent of entitled " a kind of preparation method of manganese vanadate nano belt " disclose one
Plant manganese vanadate nano belt, consisting of Mn2V2O7, currently, with respect to the research of manganese vanadate nano material, its composition focuses primarily upon
MnV2O6、b-Mn2V2O7、MnV2O5Mainly have stratiform, tiltedly side etc. on, structure, however, for nano material, its composition, pattern and
Preparation method etc. is all closely related with performance, and therefore, the different composition of exploitation, the manganese vanadate nano material of different-shape are to material
Diversified, potential functional diversities are significant, are badly in need of breaking through.
Content of the invention
The technical problem to be solved in the present invention is to provide that a kind of synthesis technique is simple, the manganese vanadate nano material of function admirable
And its synthetic method and application, using one step hydro thermal method, throw in the temperature of ratio, reaction system pH, reaction by regulating and controlling raw material
And the reaction condition such as time, mixing speed, so that manganese, vanadium, oxygen mix on a molecular scale, prepares MnV12O31·10H2O receives
Rice noodle；Further with " dipping-dry " method by conducting polymer Polyglycolic acid fibre-polystyrolsulfon acid（PEDOT-
PSS）It is coated on MnV12O31·10H2The top layer of O nano wire obtains modified nano material MnV of complex12O31·10H2O/
PEDOT-PSS, and by MnV12O31·10H2O nano wire and nano material MnV of complex modification12O31·10H2O/PEDOT-
PSS is applied in lithium ion battery as positive electrode.
The technical solution used in the present invention is：A kind of manganese vanadate nano material, the consisting of of described manganese vanadate nano material
MnV12O31·10H2O, pattern is the nano wire of diameter 50-100nm.
The synthetic method of above-mentioned manganese vanadate nano material, comprises the following steps：
1. manganese chloride, the aqueous solution of ammonium metavanadate are prepared respectively, by ammonium metavanadate：The mol ratio of manganese chloride is 1-2：1,
Add under stirring, by ammonium metavanadate aqueous solution in manganese chloride aqueous solution, make reaction system；
2. adjusting reaction system pH is 1-2, proceeds to reactor and seals, and with 110-160 DEG C, reaction 1-6h, obtains crude product
Solution；
3. the solution of step 2. middle crude product is cooled to room temperature, washing, is dried, obtain manganese vanadate MnV12O31·10H2O receives
Rice noodle.
The concentration of described manganese chloride aqueous solution is 0.01-1mol/L.
The present invention also provides above-mentioned manganese vanadate MnV12O31·10H2O nano material is as positive electrode in lithium ion battery
Application.
A kind of complex modification manganese vanadate nano material, including MnV12O31·10H2The sandwich layer of O nano wire and being coated on
MnV12O31·10H2The top layer of the PEDOT-PSS of sandwich layer periphery of O nano wire.
Described MnV12O31·10H2A diameter of 50-100nm of O nano wire.
A kind of preparation method of complex modification manganese vanadate nano material, comprises the following steps：
1. manganese chloride, the aqueous solution of ammonium metavanadate are prepared respectively, by ammonium metavanadate：The mol ratio of manganese chloride is 1-2：1,
Add under stirring, by ammonium metavanadate aqueous solution in manganese chloride aqueous solution, make reaction system；
2. adjusting reaction system pH is 1-2, proceeds to reactor and seals, and with 110-160 DEG C, reaction 1-6h, obtains crude product
Solution；
3. the solution of step 2. middle crude product is cooled to room temperature, washing, is dried, obtain manganese vanadate MnV12O31·10H2O receives
Rice noodle；
4. with dipping-oven drying method in nano wire outer layer covers PEDOT-PSS：By manganese vanadate nano wire press mass concentration 1% ~
25% is scattered in DMF solution, forms manganese vanadate dispersion liquid, and under agitation, Deca PEDOT-PSS is to vanadic acid
Manganese dispersion liquid, controls PEDOT-PSS to be 1 with the mass ratio of dispersion liquid:10～1:1, stir 10 ~ 60min, be centrifuged, be dried, must answer
Polymer modified manganese vanadate nano material MnV12O31·10H2O/PEDOT-PSS.
Preferably, 5. described preparation method also includes step：By MnV12O31·10H2O/PEDOT-PSS presses mass concentration 1%
~ 25% is scattered in DMF solution, forms MnV12O31·10H2O/PEDOT-PSS dispersion liquid, under agitation to
MnV12O31·10H2O/PEDOT-PSS dispersion liquid Deca PEDOT-PSS, controls PEDOT-PSS to be 1 with the mass ratio of dispersion liquid:
10～1:1, stir 10 ~ 60min, be centrifuged, be dried, obtain the MnV of top layer thickening12O31·10H2O/PEDOT-PSS；Repeat step is 5.
1-3 time.
Described PEDOT-PSS specification is PH1000.
The present invention also provides above-mentioned complex modification manganese vanadate nano material MnV12O31·10H2O/PEDOT-PSS is as just
Application in lithium ion battery for the pole material.
Technique scheme is to prepare nano material by one step hydro thermal method, first, prepares manganese vanadate MnV12O31·10H2O
Nano wire, in building-up process, controls ammonium metavanadate and manganese chloride mol ratio to be 1-2：1, by ammonium metavanadate aqueous solution under agitation
Drop in manganese chloride aqueous solution, mixing speed keeps vorticity with reaction system, specifically optional 200-1500 turn/
Point；Adjust reaction system pH for after 1-2, continuing stirring 5-15min, proceed to reactor airtight, 110-160 DEG C, reaction 1-6h,
Obtain the solution containing crude product；Treat that the solution of crude product is cooled to room temperature, first centrifugation, then with deionized water, anhydrous second
Alcohol washs 3-5 time respectively, finally dries, in the method reaction system homogeneous it is achieved that manganese, vanadium, oxygen on a molecular scale
Mixing, obtains a diameter of 50-100nm, length is micron-sized manganese vanadate MnV12O31·10H2O nano wire.Further, by vanadic acid
Manganese MnV12O31·10H2O nano wire presses mass concentration 1% ~ 25% by ultrasonic disperse in N,N-dimethylformamide（DMF）Solution
In, form uniform manganese vanadate dispersion liquid, under agitation, PEDOT-PSS solution is slowly dropped to manganese vanadate dispersion liquid, stirring
10 ~ 60min, centrifugation precipitates and is dried, and obtains complex modification manganese vanadate nano material MnV12O31·10H2O/PEDOT-
PSS, this material is with above-mentioned MnV12O31·10H2O nano wire, as sandwich layer, by carrying out " dipping-dry " step, will conductive gather
Compound PEDOT-PSS is coated on MnV12O31·10H2The periphery formation top layer of O nano wire, obtains complex modification manganese vanadate nanometer
Material MnV12O31·10H2O/PEDOT-PSS.For increasing the thickness of top layer PEDOT-PSS, can further above-mentioned complex be changed
Property manganese vanadate nano material MnV12O31·10H2O/PEDOT-PSS is scattered in DMF again, and Deca PEDOT-PSS, that is, repeat into
Row " dipping-dry " step, when impregnating every time, the PEDOT-PSS that control is newly added dropwise to the mass ratio of corresponding dispersion liquid is
1:10～1:1, the thickness on top layer is relevant with the number of repetition of the amount of Deca and dipping-drying operation, thus obtaining required answering
Polymer modified nano material MnV12O31·10H2O/PEDOT-PSS.Wherein, PEDOT-PSS is a kind of very high height of conductivity
The aqueous solution of Molecularly Imprinted Polymer, PEDOT in varing proportions can get the different aqueous solution of conductivity from PSS, using manganese vanadate
The structural stability of vanadic acid manganese material can be strengthened with the synergism of conducting polymer conjugated structure, finally, by research electrification
Learn performance, by MnV12O31·10H2O nano wire and nano material MnV of complex modification12O31·10H2O/PEDOT-PSS makees
It is applied in lithium ion battery for positive electrode.
The invention has the beneficial effects as follows：（1）The invention provides MnV12O31·10H2O nano wire and modified the receiving of complex
Rice material MnV12O31·10H2O/PEDOT-PSS and its synthetic method and application, expand and enrich manganese vanadate nano material and lithium
The species of ion battery material；（2）Using one step hydro thermal method, synthetic method craft is simple, condition is controlled, and prepared product is pure
Only, size uniformity, appearance structure is easily controllable；（3）Any surfactant or organic formwork agent is not required the use of in building-up process,
Environmental friendliness；（4）Suitable batch produces, and is that applied research establishes good technique basis.
With reference to specific embodiment, the present invention is described in detail.
Brief description
Fig. 1 is the MnV being obtained according to embodiment 112O31·10H2X-ray diffraction (XRD) figure of O nano wire；
Fig. 2 is the MnV being obtained according to embodiment 112O31·10H2Scanning electron microscope analysis (SEM) figure of O nano wire；
Fig. 3 is the MnV being obtained according to embodiment 212O31·10H2X-ray diffraction (XRD) figure of O nano wire；
Fig. 4 is the MnV being obtained according to embodiment 212O31·10H2Scanning electron microscope analysis (SEM) figure of O nano wire；
Fig. 5 is the MnV being obtained according to embodiment 312O31·10H2X-ray diffraction (XRD) figure of O nano wire；
Fig. 6 is the MnV being obtained according to embodiment 312O31·10H2Scanning electron microscope analysis (SEM) figure of O nano wire；
Fig. 7 is the complex modified Nano material MnV being obtained according to embodiment 412O31·10H2The X-ray of O/PEDOT-PSS
Diffraction (XRD) figure；
Fig. 8 is the complex modified Nano material MnV being obtained according to embodiment 412O31·10H2The transmission electricity of O/PEDOT-PSS
(TEM) figure analyzed by mirror；
Fig. 9 is the MnV being obtained according to embodiment 112O31·10H2O nano wire is 50 mA/g in electric current density, and voltage range is
Discharge curve under conditions of 1.5V-3.5V, wherein abscissa represent discharge capacity, and vertical coordinate represents voltage；
Figure 10 is the complex modified Nano material MnV being obtained according to embodiment 412O31·10H2O/PEDOT-PSS is in electric current
Density is 50 mA/g, and voltage range is the discharge curve under conditions of 1.5V-3.5V, and wherein abscissa represents discharge capacity,
Vertical coordinate represents voltage.
Specific embodiment
For a better understanding of the present invention, illustrate below in conjunction with specific embodiment, but do not limit this in any form
Bright, if no special instructions, described operation is routine operation, and agents useful for same all can be obtained by commercial sources.
Embodiment 1
Ammonium metavanadate by 4mmol（NH4VO3, analyze pure）It is dissolved in 8 mL distilled water, by the manganese chloride of 2mmol
（MnCl2· 4H2O, analysis is pure）It is dissolved in 4 mL distilled water, under magnetic agitation effect, by NH4VO3Solution drops to
MnCl2In solution, make reaction system, stir 10 min, with the HNO of 1mol/L3（Analysis is pure）Solution is by the pH value of reaction system
Continue stirring 10 min after being adjusted to 2, proceed in the hydrothermal reaction kettle of 20 mL, after sealing, be placed on 120 DEG C of hydro-thermals in calorstat
Reaction 3h, be cooled to room temperature after completion of the reaction, be centrifuged and must precipitate, deionized water and dehydrated alcohol respectively by washing of precipitate 5 times,
Finally it is centrifuged and gained precipitated product is placed in baking oven, be vacuum dried 16 h in 60 DEG C, obtain manganese vanadate MnV12O31·
10H2O nano material.
Material phase analysis are carried out with X-ray diffraction method, result such as Fig. 1 it can be seen that the characteristic peak positions of product and intensity with
JCPDS-ICDD No.47-146 is substantially identical for standard card, shows that product is MnV12O31·10H2O, the characteristic strength of product is relatively
Weak, peak type is wider, shows that the degree of crystallinity of product is poor.Scanning electron microscope（SEM）Carry out morphology analysis, result such as Fig. 2, can from figure
To find out：Product is that a large amount of nano wires are intertwined the aggregation of formation, and the diameter of single nano-wire is about 50nm.
Embodiment 2
NH by 0.2mmol4VO3It is dissolved in 8 mL distilled water, by the MnCl of 0.2mmol2· 4H2O is dissolved to 4
In mL distilled water, under magnetic agitation effect, by NH4VO3Solution drops to MnCl2In solution, stir 10 min, with 1mol/L
HNO3Solution continues stirring 15 min after the pH value of reaction system is adjusted to 2, proceeds in the hydrothermal reaction kettle of 20 mL afterwards,
Be placed on 160 DEG C of hydro-thermal reactions 1h in calorstat after sealing, be cooled to room temperature after completion of the reaction, be centrifuged and must precipitate, spend from
Sub- water and dehydrated alcohol wash respectively and precipitate 3 times, and the precipitation obtaining is placed in baking oven and is vacuum dried 16 h in 60 DEG C, obtains
MnV12O31·10H2O material.Thing phase and morphology analysis result are respectively as shown in Figure 3, Figure 4 it can be seen that the feature peak position of product
Put and intensity and MnV12O31·10H2O standard card（JCPDS-ICDD No.47-146）Match.Sem analysis show product by
A large amount of nano wires are constituted, a diameter of 50-100nm of single nano-wire, and length is several microns.
Embodiment 3
NH by 8mmol4VO3It is dissolved in 8 mL distilled water, by the MnCl of 4mmol2· 4H2O is dissolved to 4 mL and steams
In distilled water, under magnetic agitation effect, by NH4VO3Solution drops to MnCl2In solution, stir 10 min, with 1mol/L's
HNO3Solution continues stirring 5 min after the pH value of reaction system is adjusted to 1, proceeds to afterwards in the hydrothermal reaction kettle of 20 mL, sealing
After be placed on 110 DEG C of hydro-thermal reactions 6h in calorstat, be cooled to room temperature after completion of the reaction, be centrifuged and must precipitate, deionized water
And dehydrated alcohol washs 5 times respectively, the precipitation obtaining is placed in baking oven and is vacuum dried 16 h in 60 DEG C, obtains MnV12O31·
10H2O material.Respectively as shown in Figure 5, Figure 6, XRD spectra result shows the intensity of product diffraction maximum for thing phase and morphology analysis result
And position and MnV12O31·10H2O standard card（JCPDS-ICDD No.47-146）Match.Sem analysis show product by big
Amount nano wire is constituted.
Embodiment 4
The MnV of Example 1 synthesis12O31·10H2O nano wire 0.1g is placed in and is dried in beaker and adds 10 mL N, N-
Dimethylformamide（DMF）, it is placed in stirring on magnetic stirring apparatuss after ultrasonic disperse is uniform, take commercially available PEDOT-PSS
（PH1000, Clevios）Solution 1mL is slowly added dropwise to above-mentioned manganese vanadate dispersion liquid, continues stirring 10min after completion of dropping,
Centrifugation, precipitation is placed in 100 in vacuum drying ovenoC is vacuum dried 10h, and PEDOT-PSS is coated on MnV12O31·10H2O
Nano wire top layer, obtains MnV12O31·10H2O/PEDOT-PSS；Take gained MnV12O31·10H2O/PEDOT-PSS and again with
DMF dispersion formed dispersion liquid, Deca PEDOT-PSS to dispersion liquid, stir 10min, centrifugation, be dried, and repeat this DMF dispersion,
Deca PEDOT-PSS to dispersion liquid, stirring and centrifugation, drying process 1 time, i.e. Deca PEDOT-PSS3 time altogether, to increase parcel
PEDOT-PSS thickness, finally obtain modified nano material MnV of required complex12O31·10H2O/PEDOT-PSS.
Material phase analysis are carried out with X-ray diffraction method, result such as Fig. 7, result shows the spy of product after cladding PEDOT-PSS
Levy diffraction maximum position not to be moved, also do not have other dephasign peaks to occur, show that PEDOT-PSS is not inserted into
MnV12O31·10H2O interlayer, to MnV12O31·10H2The structure of O nano wire does not produce obvious impact.Transmission electron microscopy
Mirror（TEM）Carry out micromorphology analysis, result such as Fig. 8, as can be seen from the figure PEDOT-PSS is in MnV12O31·10H2O nanometer
Line surface defines cladding Rotating fields, the thickness of clad between 10-30nm, averagely about 10nm.
Embodiment 5
The MnV of the 2-in-1 one-tenth of Example12O31·10H2O nano wire 2g is placed in and is dried in beaker and adds 10 mL N, N- bis-
Methylformamide（DMF）, be placed on magnetic stirring apparatuss stirring after ultrasonic disperse is uniform, take commercially available PEDOT-PSS (PH1000,
Clevios) solution 10mL is slowly added dropwise to above-mentioned dispersion liquid, continues stirring 30min after completion of dropping, after being then centrifuged for separating
It is placed in 100 in vacuum drying ovenoC is vacuum dried 10h, obtains receiving of complex modification after repeating dipping-baking step 1 time
Rice material MnV12O31·10H2O/PEDOT-PSS.
Embodiment 6
The MnV of Example 3 synthesis12O31·10H2O nano wire 0.1g is placed in and is dried in beaker and adds 10 mL N, N-
Dimethyl formamide solution（Analysis is pure）In, be placed on magnetic stirring apparatuss stirring after ultrasonic disperse is uniform, after take commercially available
PEDOT-PSS (PH1000, Clevios) solution 3mL is slowly added dropwise to above-mentioned dispersion liquid, continues stirring after completion of dropping
60min, is placed in 100 in vacuum drying oven after being then centrifuged for separatingoC is vacuum dried 10h, repeats dipping-baking step 2 times
Obtain modified nano material MnV of complex afterwards12O31·10H2O/PEDOT-PSS.
Application Example 1
The MnV being prepared with embodiment 112O31·10H2The manganese vanadate nano material testing the present invention as a example O nano wire should
Chemical property for anode material for lithium-ion batteries.
This test is to be realized by being assembled into experimental cell, by MnV12O31·10H2O nano wire（80 wt%）, acetylene
Black（10 wt%）And ptfe emulsion（PTFE）（10 wt%）Working electrode is made after being sufficiently mixed；Made with metal lithium sheet
It is to electrode and reference electrode；Porous polypropylene paper is barrier film；The LiPF of 1M6, ethylene carbonate（EC）And dimethyl carbonate
（DMC）For electrolyte.By the battery test system of computer controls after battery is sealed（Wuhan Lan electricity Electronics Co., Ltd.,
LAND2001CT-1mA）Carry out charge-discharge performance test.
At ambient temperature, constant current charge-discharge circulation is carried out in 1.5V ~ 3.5 V interval with 50mA/g electric current density
Test result as shown in Figure 9, as can be seen from the figure MnV12O31·10H2The discharge capacity first of O nano wire is 155.4
MAh/g, the discharge capacity of the 2nd week is 135.3 mAh/g, the discharge capacity after circulating the 10th, 20,30 weeks respectively 132.7,
126.5 and 125.7 mAh/g.
Application Example 2
The MnV being prepared with embodiment 412O31·10H2The complex modification of the present invention is tested as a example O/PEDOT-PSS
Nano material MnV12O31·10H2O/PEDOT-PSS is applied to the chemical property of anode material for lithium-ion batteries.Method of testing
With Application Example 1.
At ambient temperature, constant current charge-discharge circulation is carried out in 1.5V ~ 3.5 V interval with 50mA/g electric current density
Test result as shown in Figure 10, as can be seen from the figure MnV12O31·10H2The putting first of O/PEDOT-PSS composite
Capacitance is 228.6 mAh/g, and the discharge capacity of the 2nd week is 180.3 mAh/g, the discharge capacity after circulating the 10th, 20,30 weeks
It is respectively 177.6,164.6 and 164.1mAh/g, its discharge capacity is above the MnV of uncoated PEDOT-PSS12O31·10H2O
Nano wire, shows that PEDOT-PSS has facilitation for the chemical property improving material.
To sum up, manganese vanadate MnV of the present invention12O31·10H2O nano wire and nano material MnV of complex modification12O31·
10H2O/PEDOT-PSS has expanded the research range of existing lithium ion battery electrode material, to design and development novel high-performance
Anode material for lithium-ion batteries is significant.
Claims (5)
1. a kind of synthesis manganese vanadate nano material method, described manganese vanadate nano material consist of MnV12O31·10H2O, shape
Looks are the nano wire of diameter 50-100nm it is characterised in that the method comprising the steps of：
1. manganese chloride, the aqueous solution of ammonium metavanadate are prepared respectively, by ammonium metavanadate：The mol ratio of manganese chloride is 1-2：1, in stirring
Under, ammonium metavanadate aqueous solution is added in manganese chloride aqueous solution, make reaction system；
2. adjusting reaction system pH is 1-2, proceeds to reactor and seals, and with 110-160 DEG C, reaction 1-6h, obtains the molten of crude product
Liquid；
3. the solution of step 2. middle crude product is cooled to room temperature, washing, is dried, obtain manganese vanadate MnV12O31·10H2O nano wire.
2. according to claim 1 a kind of synthesis manganese vanadate nano material method it is characterised in that：Described manganese chloride water
The concentration of solution is 0.01-1mol/L.
3. a kind of preparation method of complex modification manganese vanadate nano material, described complex modification manganese vanadate nano material includes
MnV12O31·10H2The sandwich layer of O nano wire and be coated on MnV12O31·10H2The PEDOT-PSS's of sandwich layer periphery of O nano wire
Top layer, described MnV12O31·10H2A diameter of 50-100nm of O nano wire is it is characterised in that comprise the following steps：
1. manganese chloride, the aqueous solution of ammonium metavanadate are prepared respectively, by ammonium metavanadate：The mol ratio of manganese chloride is 1-2：1, in stirring
Under, ammonium metavanadate aqueous solution is added in manganese chloride aqueous solution, make reaction system；
2. adjusting reaction system pH is 1-2, proceeds to reactor and seals, and with 110-160 DEG C, reaction 1-6h, obtains the molten of crude product
Liquid；
3. the solution of step 2. middle crude product is cooled to room temperature, washing, is dried, obtain manganese vanadate MnV12O31·10H2O nano wire；
4. with dipping-oven drying method in nano wire outer layer covers PEDOT-PSS：Manganese vanadate nano wire is pressed 1% ~ 25% point of mass concentration
Dissipate in DMF solution, form manganese vanadate dispersion liquid, under agitation, Deca PEDOT-PSS divides to manganese vanadate
Dispersion liquid, controls PEDOT-PSS to be 1 with the mass ratio of dispersion liquid:10～1:1, stir 10 ~ 60min, be centrifuged, be dried, obtain complex
Modified manganese vanadate nano material MnV12O31·10H2O/PEDOT-PSS.
4. a kind of preparation method of complex modification manganese vanadate nano material according to claim 3 is it is characterised in that go back
Including step 5.：By MnV12O31·10H2It is molten that O/PEDOT-PSS is scattered in N,N-dimethylformamide by mass concentration 1% ~ 25%
In liquid, form MnV12O31·10H2O/PEDOT-PSS dispersion liquid, under agitation to MnV12O31·10H2O/PEDOT-PSS disperses
Drop adds PEDOT-PSS, controls PEDOT-PSS to be 1 with the mass ratio of dispersion liquid:10～1:1, stir 10 ~ 60min, be centrifuged, do
Dry, obtain the MnV of top layer thickening12O31·10H2O/PEDOT-PSS；Repeat step 5. 1-3 time.
5. the preparation method of a kind of complex modification manganese vanadate nano material according to claim 3 or 4, its feature exists
In described PEDOT-PSS specification is PH1000.
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| CN106207130A (en) * | 2016-08-31 | 2016-12-07 | 华中科技大学 | A kind of lithium battery nickelic positive electrode of surface modification and preparation method thereof |
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| CN108281553B (en) * | 2018-01-10 | 2021-08-06 | 苏州大学 | Tungsten oxide nanorod coated with poly (3, 4-ethylenedioxythiophene), and preparation method and application thereof |
| CN110350186A (en) * | 2019-07-09 | 2019-10-18 | 齐鲁工业大学 | A kind of preparation method of novel water system Zinc ion battery positive electrode |
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