CN103943375A - Interlayer manganese dioxide/polyaniline composite material and preparation method thereof - Google Patents
Interlayer manganese dioxide/polyaniline composite material and preparation method thereof Download PDFInfo
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- CN103943375A CN103943375A CN201410193973.1A CN201410193973A CN103943375A CN 103943375 A CN103943375 A CN 103943375A CN 201410193973 A CN201410193973 A CN 201410193973A CN 103943375 A CN103943375 A CN 103943375A
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- manganese dioxide
- composite material
- potassium permanganate
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- polyaniline
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000011229 interlayer Substances 0.000 title abstract description 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 28
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000007772 electrode material Substances 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 239000010410 layer Substances 0.000 abstract description 8
- 239000008367 deionised water Substances 0.000 abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 7
- 239000003990 capacitor Substances 0.000 abstract description 5
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 43
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 10
- 238000000967 suction filtration Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 241000446313 Lamella Species 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000010406 interfacial reaction Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
-
- 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)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention relates to an interlayer manganese dioxide/polyaniline composite material and a preparation method thereof, and belongs to the field of novel energy materials. The preparation method includes the steps: dissolving aniline in organic solvent to obtain aniline organic solution, dissolving potassium permanganate in deionized water to obtain potassium permanganate water solution, controlling a pH (potential of hydrogen) value of the potassium permanganate water solution, and respectively performing low-temperature pretreatment for the aniline organic solution and the potassium permanganate water solution; leading the potassium permanganate water solution into the surface of the aniline organic solution to form a two-phase interface, and reacting for 12-48 hours under the condition of 0-4 DEG C; filtering, washing and drying a product to obtain the interlayer manganese dioxide/polyaniline composite material. Oxidized and polymerized polyaniline has high conductivity under the acidic condition and is positioned between manganese dioxide slice layers, so that reunion of the polyaniline is effectively prevented, performances such as high specific capacitance are greatly played, and a foundation is laid for the polyaniline in application to super-capacitor electrode materials.
Description
Technical field
The invention belongs to novel energy Material Field, be specifically related to a kind of sandwich-like manganese dioxide/polyaniline composite material and preparation method thereof.
Background technology
Ultracapacitor, as a kind of novel energy storage element, has the many merits such as efficiency for charge-discharge is high, service life cycle length, green non-pollution, has broad application prospects in fields such as mobile communication, electric automobile, Aero-Space.Since it is suggested, just receive the concern in the world.Ultracapacitor is divided into double electric layer capacitor and Faraday pseudo-capacitance device according to energy storage mechanism, and main electrode material has material with carbon element, transition-metals and their oxides, conducting polymer and composite material.
Manganese dioxide is high theoretical than electric capacity and energy density because having, and has abundant reserves at nature simultaneously, is the ideal material as electrode of super capacitor.But there are many problems to be solved in manganese dioxide: (1) manganese dioxide particle is easily reunited and caused actual capacity much smaller than theoretical capacity; (2) with respect to other bi-materials, the electronic conductivity of manganese dioxide is lower, causes capacitor internal resistance excessive, easily heating, and capacitance fade is too fast simultaneously.Therefore be, current focus by the composite material of preparing high-ratio surface, high conductivity with other material compound materials.Under acid condition, the polyaniline of doped polymeric has very high conductivity, is the compound optimal selection of manganese dioxide.
Summary of the invention
The object of the present invention is to provide a kind of high performance sandwich-like manganese dioxide/polyaniline composite material and preparation method thereof, manganese dioxide lamella and polyaniline are alternately superposeed and make sandwich-like manganese dioxide/polyaniline composite material, under acid condition, the polyaniline that doped polymeric generates has improved the conductivity of composite material greatly, simultaneously polyaniline layer has effectively suppressed the reunion of manganese dioxide lamella, has given full play to the performance such as high specific capacitance of manganese dioxide.
For achieving the above object, the present invention adopts following technical scheme:
A kind of preparation method of sandwich-like manganese dioxide/polyaniline composite material, using aniline organic solution as organic phase, potassium permanganate acidic aqueous solution is as inorganic phase, adopt organic and inorganic interfacial reaction, under cryogenic conditions, react a period of time, last suction filtration, washing, the dry manganese dioxide/polyaniline composite material replacing layer by layer of having prepared.
Particularly, a kind of preparation method of sandwich-like manganese dioxide/polyaniline composite material, aniline is dissolved in and in organic solvent, obtains aniline organic solution, potassium permanganate is dissolved in and in deionized water, obtains potassium permanganate solution, two kinds of solution are carried out respectively to low temperature preliminary treatment, and to regulate the pH value of potassium permanganate solution be 1 ~ 4; Potassium permanganate solution is introduced into aniline organic solution surface, forms two-phase interface, under 0-4 DEG C of condition, react 12-48 hour; Product after filtration, washing, the dry sandwich-like manganese dioxide/polyaniline composite material that makes.
Described organic solvent is one or more in carbon tetrachloride, toluene, dichlorotoleune.
In aniline organic solution, the volume ratio of aniline and organic solvent is: 1-10:100.
The concentration of potassium permanganate solution is 0.001 ~ 0.01mg/mL.
Described low temperature preliminary treatment is for sealing solution, be positioned over 0 ~ 5 DEG C of K cryogenic treatment 30 ~ 50min.
The application of sandwich-like manganese dioxide/polyaniline composite material that preparation method as above makes, is specially the electrode material as ultracapacitor.
Beneficial effect of the present invention is:
(1) under acid condition, the polyaniline that doped polymeric generates has good conductivity, utilize organic and inorganic interfacial reaction, the manganese dioxide/polyaniline composite material of preparation sandwich-like, has effectively suppressed the agglomeration of manganese dioxide in cycle charge discharge electric process simultaneously;
(2) due to manganese dioxide and the polyaniline synergy between layer by layer, composite material has the performance such as high conductivity, high specific capacitance, for its application at electrode material for super capacitor is laid a good foundation.
Brief description of the drawings
Fig. 1 is the TEM figure of the manganese dioxide/polyaniline composite material of the sandwich-like that makes of example 1;
Fig. 2 is the FT-IR figure of the manganese dioxide/polyaniline composite material of the sandwich-like that makes of example 1;
Fig. 3 is the charge-discharge figure of the manganese dioxide/polyaniline composite material of the sandwich-like that makes of example 1.
Embodiment
The present invention further illustrates the present invention with the following example, but protection scope of the present invention is not limited to the following example.
A preparation method for sandwich-like manganese dioxide/polyaniline composite material, concrete steps are:
(1) measure aniline (through 2 distilations), be dissolved in 100mL organic solvent, be mixed with the organic solution of respective concentration;
(2) weigh potassium permanganate solid, be dissolved in 100mL deionized water, and use sulphur acid for adjusting pH, be mixed with the aqueous solution of respective concentration;
(3) the above-mentioned solution preparing is positioned over to (0 ~ 5 DEG C) preliminary treatment 30 ~ 50min under cryogenic conditions, then liquor potassic permanganate is slowly introduced in aniline organic solution, form after stable organic and inorganic solution, be placed under 0-4 DEG C of condition, reaction 12-48h;
(4) by above-mentioned solution suction filtration, washing, dry, obtain end product.
embodiment 1
(1) measure 1mL aniline monomer, be dissolved in the carbon tetrachloride organic solvent of 100mL, obtain aniline organic solution;
(2) weigh 0.1mg potassium permanganate solid, be dissolved in the deionized water of 100mL, obtain the potassium permanganate solution of 0.001mg/mL, regulating pH value with the concentrated sulfuric acid is 3;
(3) above-mentioned solution is placed in to preliminary treatment 30min under 0 ~ 5 DEG C of condition, then potassium permanganate solution is introduced into aniline organic solution surface, form organic-inorganic solution; Be placed in again under 0 DEG C of condition reaction 24h;
(4) by solution suction filtration obtained above, washing, dry, obtain end product, be sandwich-like manganese dioxide/polyaniline composite material.
embodiment 2
(1) measure 2mL aniline monomer, be dissolved in the carbon tetrachloride organic solvent of 100mL, obtain aniline organic solution;
(2) weigh 1mg potassium permanganate solid, be dissolved in the deionized water of 100mL, obtain the potassium permanganate solution of 0.01mg/mL, regulating pH value with the concentrated sulfuric acid is 3;
(3) above-mentioned solution is all placed in to preliminary treatment 40min under 0 ~ 5 DEG C of condition, then potassium permanganate solution is introduced to aniline organic solution surface, form organic-inorganic solution; Be placed in again under 4 DEG C of conditions reaction 48h;
(4) by solution suction filtration obtained above, washing, dry, obtain end product, be sandwich-like manganese dioxide/polyaniline composite material.
embodiment 3
(1) measure 10mL aniline monomer, be dissolved in the carbon tetrachloride organic solvent of 100mL, obtain aniline organic solution;
(2) weigh 0.2mg potassium permanganate solid and estimate, be dissolved in the deionized water of 100mL, obtain the potassium permanganate solution of 0.002mg/mL, regulating pH value with the concentrated sulfuric acid is 3;
(3) above-mentioned solution is all placed in to preliminary treatment 30min under 0 ~ 5 DEG C of condition, then potassium permanganate solution is introduced to aniline organic solution surface, form organic-inorganic solution; Be placed in again under 2 DEG C of conditions reaction 12h;
(4) by solution suction filtration obtained above, washing, dry, obtain end product, be sandwich-like manganese dioxide/polyaniline composite material.
embodiment 4
(1) measure 1mL aniline monomer, be dissolved in the carbon tetrachloride organic solvent of 100mL, obtain aniline organic solution;
(2) weigh 0.5mg potassium permanganate solid, be dissolved in the deionized water of 100mL, obtain the potassium permanganate solution of 0.005mg/mL, regulating pH value with the concentrated sulfuric acid is 1;
(3) above-mentioned solution is all placed in to preliminary treatment 30min under 0 ~ 5 DEG C of condition, then potassium permanganate solution is introduced to aniline organic solution surface, form organic-inorganic solution; Be placed in again under 0 DEG C of condition reaction 24h;
(4) by solution suction filtration obtained above, washing, dry, obtain end product, be sandwich-like manganese dioxide/polyaniline composite material.
Sandwich-like manganese dioxide/polyaniline composite material that embodiment 1 is made carries out transmission electron microscope scanning sign, Fourier-infrared spectrum characterization, charge-discharge sign; Fig. 1 shows that unformed polyaniline molecule chain is along manganese dioxide layer growth, and then has constructed the structure in interlayer; 524cm in Fig. 2
-1for Mn-O-Mn absworption peak in manganese dioxide, 1050 cm
-1for the C-H stretching vibration absworption peak in polyaniline, 1412 cm
-1with 1635 cm
-1be respectively the vibration absorption peak of phenyl ring and quinoid ring, 1635 cm
-1for the C=N vibration absorption peak in polyaniline, 3425cm
-1be in N-H and hydrone-absworption peak of OH is common to be formed, and shows to have generated manganese dioxide/Polyaniline; As can be seen from Figure 3, the electrode of preparing with sandwich-like manganese dioxide/polyaniline composite material has good charge-discharge performance, and under the current density of 0.1A/g, electric capacity can reach 192.8F/g.
The foregoing is only preferred embodiment of the present invention, all equalizations of doing according to the present patent application the scope of the claims change and modify, and all should belong to covering scope of the present invention.
Claims (5)
1. a preparation method for sandwich-like manganese dioxide/polyaniline composite material, is characterized in that: first aniline organic solution, potassium permanganate solution are carried out to low temperature preliminary treatment, and to regulate the pH value of potassium permanganate solution be 1 ~ 4; Then potassium permanganate solution is introduced into aniline organic solution surface, forms two-phase interface, under 0-4 DEG C of condition, react 12-48 hour; Product after filtration, washing, the dry sandwich-like manganese dioxide/polyaniline composite material that makes.
2. the preparation method of sandwich-like manganese dioxide/polyaniline composite material according to claim 1, is characterized in that: in aniline organic solution, the volume ratio of aniline and organic solvent is: 1-10:100.
3. the preparation method of sandwich-like manganese dioxide/polyaniline composite material according to claim 1, is characterized in that: the concentration of potassium permanganate solution is 0.001 ~ 0.01mg/mL.
4. the preparation method of sandwich-like manganese dioxide/polyaniline composite material according to claim 1, is characterized in that: described low temperature preliminary treatment is processed 30 ~ 50min for solution is sealed, is positioned over 0 ~ 5 DEG C.
5. the application of sandwich-like manganese dioxide/polyaniline composite material that preparation method according to claim 1 makes, is characterized in that: as the electrode material of ultracapacitor.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410193973.1A CN103943375B (en) | 2014-05-09 | 2014-05-09 | A kind of sandwich-like manganese dioxide/polyaniline composite material and preparation method thereof |
| PCT/CN2015/070020 WO2015169104A1 (en) | 2014-05-09 | 2015-01-04 | Sandwich-like manganese dioxide/polyaniline composite material and preparation method therefor |
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| CN201410193973.1A CN103943375B (en) | 2014-05-09 | 2014-05-09 | A kind of sandwich-like manganese dioxide/polyaniline composite material and preparation method thereof |
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| CN103943375A true CN103943375A (en) | 2014-07-23 |
| CN103943375B CN103943375B (en) | 2016-10-05 |
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| CN (1) | CN103943375B (en) |
| WO (1) | WO2015169104A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015169104A1 (en) * | 2014-05-09 | 2015-11-12 | 福州大学 | Sandwich-like manganese dioxide/polyaniline composite material and preparation method therefor |
| CN105070514A (en) * | 2015-07-06 | 2015-11-18 | 常州大学 | Preparing polyaniline/graphene/manganese dioxide composite material through interface method and applying polyaniline/graphene/manganese dioxide composite material to super capacitor |
| CN106215522A (en) * | 2016-09-12 | 2016-12-14 | 福州大学 | The method of in-situ preparation nano flower-like manganese dioxide-catalyst on filtrate |
| CN110922752A (en) * | 2019-11-26 | 2020-03-27 | 武汉工程大学 | Polyaniline and manganese dioxide nano composite material and preparation method and application thereof |
| CN111627716A (en) * | 2020-04-28 | 2020-09-04 | 沈阳大学 | Porous flower spherical conductive polyaniline/MnO2Process for preparing nano composite material |
| CN112125334A (en) * | 2019-06-24 | 2020-12-25 | 厦门稀土材料研究所 | Metal oxide/carbon intercalated layer two-dimensional composite material and preparation method and application thereof |
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| CN112795052A (en) * | 2020-12-30 | 2021-05-14 | 苏州中科先进技术研究院有限公司 | Porous polyaniline nano-film loaded with nano zero-valent iron and preparation method and application thereof |
| CN114976166A (en) * | 2022-06-20 | 2022-08-30 | 中国科学技术大学 | Oxidation-resistant cation exchange membrane, preparation method thereof and oxidation-resistant membrane electrode |
| CN115612486B (en) * | 2022-10-31 | 2024-02-13 | 扬州大学 | Cobalt/manganese dioxide quantum dot with uricase-like activity and preparation method thereof |
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| CN103943375B (en) * | 2014-05-09 | 2016-10-05 | 福州大学 | A kind of sandwich-like manganese dioxide/polyaniline composite material and preparation method thereof |
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- 2014-05-09 CN CN201410193973.1A patent/CN103943375B/en active Active
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- 2015-01-04 WO PCT/CN2015/070020 patent/WO2015169104A1/en active Application Filing
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| CN1718620A (en) * | 2005-07-21 | 2006-01-11 | 华东理工大学 | Preparation method of conductive polyaniline intercalated laminated manganese dioxide nano-composite material |
| CN101696323A (en) * | 2009-10-30 | 2010-04-21 | 华南师范大学 | Method for preparing polyaniline/manganese dioxide composite material for super capacitor |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015169104A1 (en) * | 2014-05-09 | 2015-11-12 | 福州大学 | Sandwich-like manganese dioxide/polyaniline composite material and preparation method therefor |
| CN105070514A (en) * | 2015-07-06 | 2015-11-18 | 常州大学 | Preparing polyaniline/graphene/manganese dioxide composite material through interface method and applying polyaniline/graphene/manganese dioxide composite material to super capacitor |
| CN105070514B (en) * | 2015-07-06 | 2017-10-20 | 常州大学 | Interface method prepares polyaniline/graphene/manganese dioxide composite material applied to ultracapacitor |
| CN106215522A (en) * | 2016-09-12 | 2016-12-14 | 福州大学 | The method of in-situ preparation nano flower-like manganese dioxide-catalyst on filtrate |
| CN106215522B (en) * | 2016-09-12 | 2018-04-13 | 福州大学 | The method of in-situ preparation nano flower-like manganese dioxide-catalyst on filtrate |
| CN112125334A (en) * | 2019-06-24 | 2020-12-25 | 厦门稀土材料研究所 | Metal oxide/carbon intercalated layer two-dimensional composite material and preparation method and application thereof |
| CN110922752A (en) * | 2019-11-26 | 2020-03-27 | 武汉工程大学 | Polyaniline and manganese dioxide nano composite material and preparation method and application thereof |
| CN110922752B (en) * | 2019-11-26 | 2022-03-01 | 武汉工程大学 | Polyaniline and manganese dioxide nano composite material and preparation method and application thereof |
| CN111627716A (en) * | 2020-04-28 | 2020-09-04 | 沈阳大学 | Porous flower spherical conductive polyaniline/MnO2Process for preparing nano composite material |
| CN111627716B (en) * | 2020-04-28 | 2022-06-10 | 沈阳大学 | Porous flower spherical conductive polyaniline/MnO2Process for preparing nano composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103943375B (en) | 2016-10-05 |
| WO2015169104A1 (en) | 2015-11-12 |
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