CN102295776A - Polypyrrole-manganese dioxide composite electrode material and preparation method thereof - Google Patents
Polypyrrole-manganese dioxide composite electrode material and preparation method thereof Download PDFInfo
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- CN102295776A CN102295776A CN201110172528A CN201110172528A CN102295776A CN 102295776 A CN102295776 A CN 102295776A CN 201110172528 A CN201110172528 A CN 201110172528A CN 201110172528 A CN201110172528 A CN 201110172528A CN 102295776 A CN102295776 A CN 102295776A
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Abstract
The invention relates to the preparation of electrode materials, and specifically relates to a polypyrrole-manganese dioxide composite electrode material and a preparation method thereof. The method comprises steps that: (1) an aqueous solution of permanganate is prepared, and a protonic acid solution of pyrrole monomers is prepared; (2) the aqueous solution of permanganate is dropped into the protonic acid solution of pyrrole monomers; the mixture is subject to a reaction while being stirred; the reaction product is washed by using water and an organic solvent; and the washed product is dried, such that the polypyrrole-manganese dioxide composite electrode material is obtained. According to the invention, polypyrrole is prepared through oxidization by using permanganate, such that a polypyrrole-manganese dioxide composite electrode material formed through effective combinations at a molecular level can be obtained. Compared to a traditional mechanical mixing method and a finished product titanium dioxide surface polymerization method, the method provided by the invention provides a better composition effect. With the method, effective combination can be formed at a molecular level. Compared to prior manganese dioxide or polypyrrole materials, the electrode material provided by the present invention is effectively improved in conductivity and circulation life.
Description
Technical field
The present invention relates to the electrode materials preparation field, particularly, the present invention relates to a kind of polypyrrole-manganese dioxide composite electrode material and preparation method thereof.
Background technology
Electrical condenser is a kind of electric energy storing device, but the electrical capacity of general electrical condenser is very low.The international standard of electrical capacity (SI system) unit is faraday (F), and 1F is equivalent to can store the electric weight of 1 coulomb (C) under the internal electrical potential difference of 1 volt (V), but general condenser capacity is in μ F (10
-6F) or pF (10
-12F) order of magnitude, this efficiency far for energy storage is not enough.And the electrical capacity of ultracapacitor (Supercapacitor) directly uses F to weigh as unit, thus ultracapacitor have can be comparable with battery energy storage capacity.And compare with battery, it is faster that ultracapacitor discharges and recharges, and has stronger high power discharge ability, thereby have broad application prospects.
Ultracapacitor comprises double layer capacitor and fake capacitance device two classes, their employed electrode materials differences.Wherein the electrode materials of fake capacitance device use comprises metal oxide and conductive polymers two classes.In the metal oxide electrode material, Ru
2O fake capacitance superior performance, the specific conductivity height, but, be difficult to large-scale application in production because Ru belongs to precious metal.And MnO
2Aboundresources, cheap, be widely used in chemical power source, internal resistance is big, the less shortcoming of specific storage but it has.And polypyrrole is a kind of polymer electrode material commonly used, its specific conductivity height, and specific storage is big, but cycle life is shorter with respect to metal oxide materials.Therefore, polypyrrole and these two kinds of materials of Manganse Dioxide are carried out compound, in the hope of accessing specific conductivity height, long combination electrode material of cycle life life-span.
The preparation method of polypyrrole generally is a dropping oxidizing agent in pyrrole monomer, makes its polymerization gradually.The finished product polypyrrole directly mixes with Manganse Dioxide, can't obtain effective product of mixing on the microcosmic.Bahloul etc. are at β-MnO
2The monomeric polymerization of Polythiophene is carried out on the surface, and preparation Polythiophene-manganese dioxide composite electrode (A.Bahloul, B.Nessark, F.Habelhames and C.M.Julien, Ionics 2011,17,239-246.).Simultaneously in application number is 200910193470.3 application documents, but adopt the stability and the dispersing property of the matrix material of the polyaniline/manganese dioxide that aniline monomer and permanganate prepare all to have deficiency.
Summary of the invention
The object of the present invention is to provide a kind of polypyrrole-manganese dioxide composite electrode material.
A further object of the present invention is to provide a kind of preparation method of polypyrrole-manganese dioxide composite electrode material.
According to polypyrrole-manganese dioxide composite electrode material of the present invention, the preparation method of described electrode materials may further comprise the steps:
1) aqueous solution of preparation permanganate, the protonic acid solution of preparation pyrrole monomer;
2) aqueous solution with potassium permanganate is added drop-wise in the protonic acid solution of pyrrole monomer, carries out ultrasonic agitation, reaction, and with the product water and the organic solvent washing that obtain, drying obtains polypyrrole-manganese dioxide composite electrode material.
According to polypyrrole-manganese dioxide composite electrode material of the present invention, protonic acid is one or more in hydrochloric acid, sulfuric acid, the nitric acid in the described step 1), and described permanganate is potassium permanganate or sodium permanganate.
According to polypyrrole-manganese dioxide composite electrode material of the present invention, the concentration that described pyrrole monomer is dissolved in behind the protonic acid is 0.05～3mol/L.
According to polypyrrole-manganese dioxide composite electrode material of the present invention, described step 2) mol ratio of permanganate and pyrrole monomer is 1: 0.25～6 in.
According to polypyrrole-manganese dioxide composite electrode material of the present invention, described step 2) stir in and be ultrasonic agitation, the stirring reaction temperature is 0～80 ℃, reaction times is 2～24h, described organic solvent is acetone, ethanol or ether, and vacuum drying temperature is 40～120 ℃, and be 24h time of drying.
In addition, the present invention also provides a kind of preparation method of polypyrrole-manganese dioxide composite electrode material, said method comprising the steps of:
1) aqueous solution of preparation permanganate, the protonic acid solution of preparation pyrrole monomer;
2) aqueous solution with potassium permanganate is added drop-wise in the protonic acid solution of pyrrole monomer, stirring reaction, and with the product deionized water and the organic solvent washing that obtain, drying obtains polypyrrole-manganese dioxide composite electrode material.
The present invention adopts ultrasonic in-situ chemical oxidation composite algorithm, the combination electrode material that under ultrasound environments, prepares polypyrrole-Manganse Dioxide, by ultrasonic vibration at high speed for the contact of microscopic particles with mix the power that provides bigger, thereby make the compound more even more dispersion of two-phase, strengthen the interaction of two kinds of storerooms, further improved the specific conductivity and stability of matrix material with respect to existing method.
In the present invention, adopt permanganate oxidation to prepare polypyrrole, just can access at the effective bonded polypyrrole-manganese dioxide composite electrode material of molecular level.The present invention is with respect to traditional mechanical mixing and finished product titanium dioxide surface polymerization, has better composite effect, be formed with the combination of effect in the molecule aspect, the electrode materials of making effectively raises specific conductivity and cycle life with respect to original Manganse Dioxide or polypyrrole material.
Embodiment
Polypyrrole-manganese dioxide composite electrode material provided by the invention and preparation method thereof is as described in the summary of the invention part.The present invention will further illustrate substantive distinguishing features of the present invention and marked improvement by the description of following embodiment, and still, the present invention only is confined to following embodiment.
Embodiment 1
(1) oxidant potassium permanganate with 0.02mol is dissolved in the 100mL water, and wiring solution-forming A is dissolved in the 0.005mol pyrrole monomer in the hydrochloric acid of 100mL 1mol/L, wiring solution-forming B, and the mol ratio of potassium permanganate and pyrrole monomer is 4: 1 in two solution at this moment;
(2) slowly add solution A in the solution B, the control rate of addition, and in the constantly stirring down of 40kHz environment, 30 ℃ of reactions of constant temperature 6h, reaction product is filtered, and, be colourless until filtrate with deionized water and acetone repetitive scrubbing product, product after the washing at 60 ℃ of following vacuum-drying 24h, is obtained polypyrrole-manganese dioxide composite material.
Embodiment 2
(1) oxidant potassium permanganate with 0.02mol is dissolved in the 100mL water, and wiring solution-forming A is dissolved in the 0.02mol pyrrole monomer in the sulfuric acid of 100mL 0.5mol/L, wiring solution-forming B, and the mol ratio of potassium permanganate and pyrrole monomer is 1: 1 in two solution at this moment;
(2) slowly add solution A in the solution B, the control rate of addition, and in the constantly stirring down of 40kHz environment, 0 ℃ of reaction of constant temperature 24h, reaction product is filtered, and, be colourless until filtrate with deionized water and ether repetitive scrubbing product, product after the washing at 40 ℃ of following vacuum-drying 24h, is obtained polypyrrole-manganese dioxide composite material.
Embodiment 3
(1) oxidant potassium permanganate with 0.02mol is dissolved in the 100mL water, and wiring solution-forming A is dissolved in the 0.04mol pyrrole monomer in the nitric acid of 100mL 1mol/L, wiring solution-forming B, and the mol ratio of potassium permanganate and pyrrole monomer is 1: 2 in two solution at this moment;
(2) slowly add solution A in the solution B, the control rate of addition, and in the constantly stirring down of 40kHz environment, 50 ℃ of reactions of constant temperature 6h, reaction product is filtered, and, be colourless until filtrate with deionized water and ethanol repetitive scrubbing product, product after the washing at 80 ℃ of following vacuum-drying 24h, is obtained polypyrrole-manganese dioxide composite material.
Embodiment 4
(1) oxidant potassium permanganate with 0.02mol is dissolved in the 100mL water, and wiring solution-forming A is dissolved in the 0.06mol pyrrole monomer in the hydrochloric acid of 100mL 1mol/L, wiring solution-forming B, and the mol ratio of potassium permanganate and pyrrole monomer is 1: 3 in two solution at this moment;
(2) slowly add solution A in the solution B, the control rate of addition, and in the constantly stirring down of 40kHz environment, 60 ℃ of reactions of constant temperature 4h, reaction product is filtered, and, be colourless until filtrate with deionized water and ethanol repetitive scrubbing product, product after the washing at 80 ℃ of following vacuum-drying 24h, is obtained polypyrrole-manganese dioxide composite material.
Embodiment 5
(1) oxidant potassium permanganate with 0.005mol is dissolved in the 100mL water, and wiring solution-forming A is dissolved in the 0.3mol pyrrole monomer in the sulfuric acid of 100mL 0.5mol/L, wiring solution-forming B, and the mol ratio of potassium permanganate and pyrrole monomer is 1: 6 in two solution at this moment;
(2) slowly add solution A in the solution B, the control rate of addition, and in the constantly stirring down of 40kHz environment, 80 ℃ of reactions of constant temperature 2h, reaction product is filtered, and, be colourless until filtrate with deionized water and ethanol repetitive scrubbing product, product after the washing at 120 ℃ of following vacuum-drying 24h, is obtained polypyrrole-manganese dioxide composite material.
From above-mentioned all embodiment as can be seen, as long as use listed raw material in the claim, and guarantee that various parameters can produce effective electrode materials finished product in the preparation process in the listed scope of claim.In concrete implementation process, those skilled in the art can both carry out concrete enforcement according to the specialized range of each processing parameter, does not exceed with the given the foregoing description of the present invention.
By above-mentioned specific embodiment the present invention is described in detail, those skilled in the art are to be understood that, in the scope that does not exceed spirit of the present invention and essence, certain modification and distortion to the present invention makes still can realize result of the present invention.
Claims (10)
1. a polypyrrole-manganese dioxide composite electrode material is characterized in that, the preparation method of described electrode materials may further comprise the steps:
1) aqueous solution of preparation permanganate, the protonic acid solution of preparation pyrrole monomer;
2) aqueous solution with potassium permanganate is added drop-wise in the protonic acid solution of pyrrole monomer, carries out ultrasonic agitation, reaction, and with the product water and the organic solvent washing that obtain, drying obtains polypyrrole-manganese dioxide composite electrode material.
2. according to the described polypyrrole-manganese dioxide composite electrode material of claim 1, it is characterized in that protonic acid is one or more in hydrochloric acid, sulfuric acid, the nitric acid in the described step 1), described permanganate is potassium permanganate or sodium permanganate.
3. according to the described polypyrrole-manganese dioxide composite electrode material of claim 1, it is characterized in that the concentration that described pyrrole monomer is dissolved in behind the protonic acid is 0.05～3mol/L.
4. according to the described polypyrrole-manganese dioxide composite electrode material of claim 1, it is characterized in that described step 2) in the mol ratio of permanganate and pyrrole monomer be 1: 0.25～6.
5. according to the described polypyrrole-manganese dioxide composite electrode material of claim 1, it is characterized in that, described step 2) frequency of ultrasonic agitation is 40kHz in, temperature of reaction is 0～80 ℃, reaction times is 2～24h, described organic solvent is acetone, ethanol or ether, and vacuum drying temperature is 40～120 ℃, and the time is 24h.
6. the preparation method of a polypyrrole-manganese dioxide composite electrode material is characterized in that, said method comprising the steps of:
1) aqueous solution of preparation permanganate, the protonic acid solution of preparation pyrrole monomer;
2) aqueous solution with potassium permanganate is added drop-wise in the protonic acid solution of pyrrole monomer, carries out ultrasonic agitation, reaction, and with the product water and the organic solvent washing that obtain, drying obtains polypyrrole-manganese dioxide composite electrode material.
7. according to the preparation method of the described polypyrrole-manganese dioxide composite electrode material of claim 6, it is characterized in that protonic acid is one or more in hydrochloric acid, sulfuric acid, the nitric acid in the described step 1), described permanganate is potassium permanganate or sodium permanganate.
8. according to the preparation method of the described polypyrrole-manganese dioxide composite electrode material of claim 6, it is characterized in that the concentration that described pyrrole monomer is dissolved in behind the protonic acid is 0.05～3mol/L.
9. according to the preparation method of the described polypyrrole-manganese dioxide composite electrode material of claim 6, it is characterized in that described step 2) in the mol ratio of permanganate and pyrrole monomer be 1: 0.25～6.
10. according to the preparation method of the described polypyrrole-manganese dioxide composite electrode material of claim 6, it is characterized in that, described step 2) frequency of ultrasonic agitation is 40kHz in, temperature of reaction is 0～80 ℃, reaction times is 2～24h, described organic solvent is acetone, ethanol or ether, and vacuum drying temperature is 40～120 ℃, and the time is 24h.
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Cited By (7)
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| CN102583562A (en) * | 2012-02-28 | 2012-07-18 | 南京工业大学 | Preparation method of supercapacitor electrode material manganese dioxide |
| CN102924718A (en) * | 2012-11-16 | 2013-02-13 | 清华大学深圳研究生院 | Preparation method of nanostructured polypyrrole |
| CN103117175A (en) * | 2013-02-25 | 2013-05-22 | 中国科学院过程工程研究所 | Multi-element composite nano-material, preparation method thereof and application thereof |
| CN104037389A (en) * | 2014-06-19 | 2014-09-10 | 合肥国轩高科动力能源股份公司 | Transition-metal-oxide negative electrode material of lithium ion battery and preparation method of material |
| CN108281293A (en) * | 2018-01-18 | 2018-07-13 | 济南大学 | A kind of MnO2The preparation method and applications of nano wire |
| CN108373535A (en) * | 2018-03-26 | 2018-08-07 | 合肥萃励新材料科技有限公司 | A kind of synthetic method of Mn oxide load polypyrrole nanotube |
| CN113755012A (en) * | 2021-09-28 | 2021-12-07 | 安徽理工大学 | Preparation method and application of MnO2/PPy composite material with three-dimensional mesoporous microsphere structure |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583562A (en) * | 2012-02-28 | 2012-07-18 | 南京工业大学 | Preparation method of supercapacitor electrode material manganese dioxide |
| CN102583562B (en) * | 2012-02-28 | 2014-02-26 | 南京工业大学 | Preparation method of supercapacitor electrode material manganese dioxide |
| CN102924718A (en) * | 2012-11-16 | 2013-02-13 | 清华大学深圳研究生院 | Preparation method of nanostructured polypyrrole |
| CN103117175A (en) * | 2013-02-25 | 2013-05-22 | 中国科学院过程工程研究所 | Multi-element composite nano-material, preparation method thereof and application thereof |
| CN103117175B (en) * | 2013-02-25 | 2016-08-03 | 中国科学院过程工程研究所 | A kind of multiple elements design nano material, Its Preparation Method And Use |
| CN104037389A (en) * | 2014-06-19 | 2014-09-10 | 合肥国轩高科动力能源股份公司 | Transition-metal-oxide negative electrode material of lithium ion battery and preparation method of material |
| CN108281293A (en) * | 2018-01-18 | 2018-07-13 | 济南大学 | A kind of MnO2The preparation method and applications of nano wire |
| CN108373535A (en) * | 2018-03-26 | 2018-08-07 | 合肥萃励新材料科技有限公司 | A kind of synthetic method of Mn oxide load polypyrrole nanotube |
| CN113755012A (en) * | 2021-09-28 | 2021-12-07 | 安徽理工大学 | Preparation method and application of MnO2/PPy composite material with three-dimensional mesoporous microsphere structure |
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Application publication date: 20111228 |