CN103400696A - Conductive polymer ruthenium dioxide membrane electrode and preparation method thereof - Google Patents
Conductive polymer ruthenium dioxide membrane electrode and preparation method thereof Download PDFInfo
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- CN103400696A CN103400696A CN2013103273097A CN201310327309A CN103400696A CN 103400696 A CN103400696 A CN 103400696A CN 2013103273097 A CN2013103273097 A CN 2013103273097A CN 201310327309 A CN201310327309 A CN 201310327309A CN 103400696 A CN103400696 A CN 103400696A
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Abstract
The invention discloses a conductive polymer ruthenium dioxide membrane electrode and a preparation method thereof. The conductive polymer is poly-ethylenedioxythiophene, powder ruthenium dioxide is added to the conductive polymer, and tantalum sheets are adopted as electrode substrates. Prepared superfine ruthenium dioxide powder is added to the monomer solution or oxidizing agent solution, and the ruthenium dioxide powder is dispersed in the monomer solution or the oxidizing agent solution; and then the tantalum sheets are immersed into the oxidizing agent solution, subsequently, the tantalum sheets are immersed into the monomer solution, and the conductive polymer film containing ruthenium dioxide is produced on the surfaces of the tantalum sheets in a polymerizing manner. Or the prepared superfine ruthenium dioxide powder is added to the pre-polymerized poly-ethylenedioxythiophene solution, the ruthenium dioxide powder is dispersed, and the conductive polymer film containing ruthenium dioxide powder is directly coated on the surfaces of the tantalum sheets. The conductive polymer film electrodes prepared by the preparation method can be used in the temperature range of minus 55 DEG - plus 125 DEG C and can be charged and discharged infinitely.
Description
Technical field
The present invention relates to tantalum electrolytic capacitor, especially a kind of tantalum electrolytic capacitor negative electrode and preparation method thereof.
Background technology
Tantalum electrolytic capacitor, especially solid electrolyte Ta capacitor, its cathode layer are manganese dioxide, electric polypyrrole or poly-3,4-ethylene dioxythiophene.Above-mentioned three kinds of cathode materials are all the surfaces of directly decomposing or be aggregated in the tantalum capacitor tantalum anode, and formation of solid polycomplex electrolyte tantalum electrolytic capacitor.Adopt the prepared solid electrolyte Ta capacitor of above-mentioned negative electrode,, because negative electrode directly decomposes or is aggregated in the tantalum anode surface, limited by the tantalum anode volume, the capacity of negative electrode is on the low side, is difficult to the solid electrolyte tantalum electrolytic capacitor of the capacity of preparing large (more than 1mF).
In prior art, application number is that 02115770.7 invention relates to the semiconductor photoelectrocatalysielectrode technical field, particularly has visible light-responded composite membrane optoelectronic pole and preparation method thereof.Film photoelectric electrode includes the titanium substrate, is to ooze in the titanium substrate to be covered with the composite mixed titanium deoxid film layer of cobalt ruthenium, is covered with the titanium deoxid film layer outside the composite mixed titanium deoxid film layer of cobalt ruthenium again.The present invention adopts sol-gel processing to prepare film photoelectric electrode, and technique is simple, and metal ion mixing concentration is easy to regulate; The optoelectronic pole outermost layer is comprised of titanium dioxide, by outward inward energy gap diminish gradually, be conducive to different-waveband light and absorb successively, thereby fully enlarged the spectral response scope of material, and the stable performance of optoelectronic pole; Greatly be better than single homogeneous phase metal ion or grade doping at one or more aspect of performances such as light absorption, photocatalysis, opto-electronic conversion.The present invention can effectively be applied in fields such as solar energy utilization, opto-electronic conversion, photocatalysis degradation organic contaminants.Application number is that 201210370552.2 invention proposes the preparation method of a kind of energy storage with the ruthenic oxide combination electrode, it is characterized in that comprising the steps: a) the ruthenic oxide material of different content to be mixed in shear mixing equipment with binding agent, thickener, carbon and deionized water, make the multiple slurry that ruthenic oxide content is different, viscosity is different; B) slurry that ruthenic oxide content is minimum is coated on collector, drying forming; C) method coated with multiple layer slurry use step b).The ruthenic oxide combination electrode that the present invention obtains is combined tightr with collector, have the characteristics such as high power capacity and long-life, can be widely used in national defence and the energy storage field such as civilian.201210003214.5 disclosure of the invention of application number a kind of preparation method of ruthenium oxide electrode of super capacitor, belong to the preparation method of electrode for capacitors; The inventive method be coated on tantalum paper tinsel surface contain the ruthenium compound slurry in added valve metal powder and nano hydrated ruthenium-oxide, then the tantalum paper tinsel after drying is put into water vapour environment and is carried out thermal decomposition and prepare amorphous hydrated ruthenic oxide negative electrode, therefore can avoid ruthenic oxide dehydration crystallization, thus improved ruthenium oxide coatings and tantalum paper tinsel bond strength, improved the electroded specific capacity of ruthenium-oxide.Adopt the capacitor electrode of the inventive method preparation to have advantage, energy density and the power density advantages of higher such as resistance to elevated temperatures is good, the anti-vibration ability is strong; It is a kind of method for preparing ultracapacitor.Above prior art, all less than the technical problem that solves " existing solid electrolyte Ta capacitor is difficult to the capacity of preparing large (more than 1mF) because the capacity of negative electrode is on the low side solid electrolyte tantalum electrolytic capacitor ".
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of conducting polymer ruthenic oxide membrane electrode and preparation method thereof,, by with jumbo tantalum anode, being combined into jumbo conductive solid polymer electrolyte tantalum capacitor, can solve the technical problem of " existing solid electrolyte Ta capacitor is difficult to the capacity of preparing large (more than 1mF) because the capacity of negative electrode is on the low side solid electrolyte tantalum electrolytic capacitor ".
The technical solution used in the present invention: described conducting polymer ruthenic oxide membrane electrode is formed at the tantalum piece surface of tantalum capacitor, a kind of with poly-3, the poly-3,4-ethylene dioxythiophene of 4-ethylenedioxy thiophene or modification is that base material, ruthenic oxide powder disperse membrane electrode wherein.This conducting polymer materials that conducting polymer and ultrafine ruthenium oxide powder end are formed by polymerization or mechanical mixture, the ultrafine ruthenium oxide powder end is dispersed in the conducting polymer body, and its conductivity is high, and capacity is large.
The preparation method of described conducting polymer ruthenic oxide membrane electrode is: first the ruthenic oxide powder is joined in 3,4-ethylene dioxythiophene monomer solution and/or oxidizing agent solution, mix; Again the tantalum piece of having polished is immersed in the 3,4-ethylene dioxythiophene monomer solution, make tantalum piece adsorption one deck 3,4-ethylene dioxythiophene monomer; The tantalum piece that will be stained with again the 3,4-ethylene dioxythiophene monomer immerses in oxidizing agent solution, repeatedly carries out 5-20 time; Polymerization at the temperature of 0 ℃～+ 40 ℃, until the tantalum piece surface forms the poly-3,4-ethylene dioxythiophene film of the conduction that contains the ruthenic oxide powder.The solvent of described 3,4-ethylene dioxythiophene monomer solution is one or more in following material: ethanol, methyl alcohol, butyl acetate, n-butanol; The solvent of described oxidizing agent solution is one or more in following material: ethanol, methyl alcohol, n-butanol, water.
The preparation method of described conducting polymer ruthenic oxide membrane electrode also can adopt following method: first the ruthenic oxide powder is added polymerization in advance good poly-3, in 4-ethylenedioxy thiophene solution, solvent is one or more in following material: ethanol, methyl alcohol, n-butanol, butyl acetate, water; Mix; Again the tantalum piece of having polished is immersed in this solution 5-20 time repeatedly; Oven dry at normal temperatures, contain the poly-3,4-ethylene dioxythiophene film of ruthenic oxide powder conduction until the tantalum piece surface forms.
Described jumbo conductive solid polymer electrolyte tantalum capacitor, comprise tantalum anode and the chip membrane electrode that is positioned at the tantalum anode surface, and described chip membrane electrode adopts above-mentioned conducting polymer ruthenic oxide membrane electrode.
Conducting polymer ruthenic oxide membrane electrode of the present invention is conducting polymer and the ruthenic oxide powder composite film electrode that a kind of tantalum electrolytic capacitor is used, the preparation method is simple, this membrane electrode can use in the scope of-55 ℃～+ 125 ℃, can carry out unlimited discharging and recharging.The present invention utilizes the specific volume of ruthenic oxide material to increase the capacity of prepared membrane electrode, thereby prepare jumbo chip membrane electrode, again by the jumbo tantalum anode of preparation, be combined into jumbo conductive solid polymer electrolyte tantalum capacitor with the chip membrane electrode, thereby can solve well the technical problem of " solid electrolyte Ta capacitor is difficult to the solid electrolyte tantalum electrolytic capacitor of the capacity of preparing large (more than 1mF) because the capacity of negative electrode is on the low side " in prior art.
Description of drawings
Fig. 1 is conducting polymer ruthenic oxide membrane electrode generalized section;
Fig. 2 is conducting polymer ruthenic oxide membrane electrode outline drawing.
Wherein: 1, poly-3,4-ethylene dioxythiophene; 2, ruthenic oxide powder; 3, tantalum piece.
Embodiment
As shown in Figure 1 and Figure 2, described conducting polymer ruthenic oxide membrane electrode, with conductive polymer poly 3,4-ethylenedioxy thiophene 1 and ultrafine ruthenium oxide powder end 2 are by polymerization or mechanical mixture, and forming a kind of poly-3,4-ethylene dioxythiophene is that base material, ruthenic oxide powder disperse conducting polymer materials wherein, its conductivity is high, capacity is large, and is formed at tantalum piece 3 surfaces of tantalum capacitor, thereby prepares jumbo chip membrane electrode., by the jumbo tantalum anode of preparation, with the chip membrane electrode, be combined into jumbo conductive solid polymer electrolyte tantalum capacitor again.
Further illustrate the preparation method of conducting polymer ruthenic oxide membrane electrode below in conjunction with following three specific embodiments.
Embodiment one:
The ruthenic oxide powder is joined in the monomer solution of 3,4-ethylene dioxythiophene, mix; Again the tantalum piece of having polished is immersed in this solution, make tantalum piece adsorption one deck 3,4-ethylene dioxythiophene monomer; The tantalum piece that will be stained with again monomer immerses in oxidizing agent solution, repeatedly carries out 5-20 time; Polymerization at the temperature of 0 ℃～+ 40 ℃, until the tantalum piece surface forms the poly-3,4-ethylene dioxythiophene film of the conduction that contains the ruthenic oxide powder.
Embodiment two:
The ruthenic oxide powder is joined in the solution of oxidant toluenesulfonic acid iron, mix; The tantalum piece that to polish again first immerses in the 3,4-ethylene dioxythiophene monomer solution, until the tantalum piece surface forms, contains the 3,4-ethylene dioxythiophene monomer film; Then tantalum piece is immersed in oxidizing agent solution 5-20 time repeatedly; Polymerization at the temperature of 0 ℃～+ 40 ℃, until the tantalum piece surface forms the poly-3,4-ethylene dioxythiophene film of the conduction that contains the ruthenic oxide powder.
Embodiment three:
The ruthenic oxide powder is added in the solution of the good poly-3,4-ethylene dioxythiophene of polymerization in advance, mix; Again the tantalum piece of having polished is immersed in this solution 5-20 time repeatedly; Oven dry at normal temperatures, contain the poly-3,4-ethylene dioxythiophene film of ruthenic oxide powder conduction until the tantalum piece surface forms.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., within all being included in protection scope of the present invention.
Claims (7)
1. conducting polymer ruthenic oxide membrane electrode, described conducting polymer ruthenic oxide membrane electrode is formed at tantalum piece (3) surface of tantalum capacitor, it is characterized in that, described conducting polymer ruthenic oxide membrane electrode is a kind of with poly-3, the poly-3,4-ethylene dioxythiophene of 4-ethylenedioxy thiophene (1) or modification is that base material, ruthenic oxide powder (2) disperse membrane electrode wherein.
2. the preparation method of a conducting polymer ruthenic oxide membrane electrode, is characterized in that, first the ruthenic oxide powder joined in 3,4-ethylene dioxythiophene monomer solution and/or oxidizing agent solution, mixes; Again the tantalum piece of having polished is immersed in the 3,4-ethylene dioxythiophene monomer solution, make tantalum piece adsorption one deck 3,4-ethylene dioxythiophene monomer; The tantalum piece that will be stained with again the 3,4-ethylene dioxythiophene monomer immerses in oxidizing agent solution, repeatedly carries out 5-20 time; Polymerization at the temperature of 0 ℃～+ 40 ℃, until the tantalum piece surface forms the poly-3,4-ethylene dioxythiophene film of the conduction that contains the ruthenic oxide powder.
3. the preparation method of conducting polymer ruthenic oxide membrane electrode according to claim 2, is characterized in that, the solvent of described 3,4-ethylene dioxythiophene monomer solution is one or more in following material: ethanol, methyl alcohol, butyl acetate, n-butanol; The solvent of described oxidizing agent solution is one or more in following material: ethanol, methyl alcohol, n-butanol, water.
4. the preparation method of conducting polymer ruthenic oxide membrane electrode according to claim 2, is characterized in that, described oxidizing agent solution is oxidant toluenesulfonic acid ferrous solution.
5. the preparation method of a conducting polymer ruthenic oxide membrane electrode, is characterized in that, first the ruthenic oxide powder added in the good poly-3,4-ethylene dioxythiophene solution of polymerization in advance, mixes; Again the tantalum piece of having polished is immersed in this solution 5-20 time repeatedly; Oven dry at normal temperatures, contain the poly-3,4-ethylene dioxythiophene film of ruthenic oxide powder conduction until the tantalum piece surface forms.
6. the preparation method of conducting polymer ruthenic oxide membrane electrode according to claim 5, is characterized in that, the solvent of described poly-3,4-ethylene dioxythiophene solution is one or more in following material: ethanol, methyl alcohol, n-butanol, butyl acetate, water.
7. a jumbo conductive solid polymer electrolyte tantalum capacitor, comprise tantalum anode and the chip membrane electrode that is positioned at the tantalum anode surface, it is characterized in that, described chip membrane electrode is conducting polymer ruthenic oxide membrane electrode claimed in claim 1.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102426929A (en) * | 2012-01-08 | 2012-04-25 | 中国振华（集团）新云电子元器件有限责任公司 | Method for preparing ruthenium oxide electrode of super capacitor |
| CN102891013A (en) * | 2012-09-29 | 2013-01-23 | 上海奥威科技开发有限公司 | Method for preparing ruthenium dioxide combination electrode for energy storage |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102426929A (en) * | 2012-01-08 | 2012-04-25 | 中国振华（集团）新云电子元器件有限责任公司 | Method for preparing ruthenium oxide electrode of super capacitor |
| CN102891013A (en) * | 2012-09-29 | 2013-01-23 | 上海奥威科技开发有限公司 | Method for preparing ruthenium dioxide combination electrode for energy storage |
Non-Patent Citations (4)
| Title |
|---|
| LI CHEN ， CHANGZHOU YUAN ，BO GAO 等: "Microwave-assisted synthesis of organic–inorganic", 《J SOLID STATE ELECTROCHEM》 * |
| 张莉，邹积岩，宋金岩: "二氧化钌薄膜电极的制备及其性能研究", 《仪器仪表学报》 * |
| 甘卫平 等: "担电容器用担壳内壁R u O : 薄膜电极的表征及电化学性能", 《无机材料学报》 * |
| 陈黎: "聚（3，4-乙撑二氧噻吩）复合材料的制备及其电化学性质的研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅱ辑 》 * |
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