CN103400696B - A kind of conductive polymer ruthenium dioxide membrane electrode and preparation method thereof - Google Patents
A kind of conductive polymer ruthenium dioxide membrane electrode and preparation method thereof Download PDFInfo
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- CN103400696B CN103400696B CN201310327309.7A CN201310327309A CN103400696B CN 103400696 B CN103400696 B CN 103400696B CN 201310327309 A CN201310327309 A CN 201310327309A CN 103400696 B CN103400696 B CN 103400696B
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Abstract
The invention discloses a kind of conductive polymer ruthenium dioxide membrane electrode and preparation method thereof.Wherein conducting polymer is poly-ethylenedioxy thiophene, and add powder ruthenium dioxide in conducting polymer, electrode base sheet adopts tantalum piece.By adding the ultrafine ruthenium oxide powder end prepared in monomer solution or in oxidizing agent solution, and powder ruthenium dioxide is dispersed in monomer solution or in oxidizing agent solution; Then tantalum piece is immersed in oxidizing agent solution, again tantalum piece is immersed in monomer solution subsequently, under normal temperature condition, generate the conducting polymer thin film containing ruthenic oxide at tantalum piece surface aggregate.Or in the solution gathering ethylenedioxy thiophene in prepolymerization, add the ultrafine ruthenium oxide powder end prepared, and powder ruthenium dioxide is disperseed, the conducting polymer thin film of powder ruthenium dioxide is directly contained in tantalum piece surface-coated.Conducting polymer thin film electrode prepared by this method can use in the scope of-55 DEG C ~+125 DEG C, can carry out unlimited discharge and recharge.
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 is manganese dioxide, electric polypyrrole or poly-3,4-ethylene dioxythiophene.Above-mentioned three kinds of cathode materials are all Direct Resolution or the surface being aggregated in tantalum capacitor tantalum anode, and formation of solid polycomplex electrolyte tantalum electrolytic capacitor.Adopt solid electrolyte Ta capacitor prepared by above-mentioned negative electrode, due to negative electrode Direct Resolution or be aggregated in tantalum anode surface, limit by tantalum anode volume, the capacity of negative electrode is on the low side, is difficult to the solid electrolyte tantalum electrolytic capacitor of capacity of preparing large (more than 1mF).
In prior art, application number be 02115770.7 invention relate to semiconductor photoelectrocatalysielectrode technical field, particularly there is visible light-responded composite membrane optoelectronic pole and preparation method thereof.Film photoelectric electrode includes titanium substrate, is to ooze in titanium substrate to be covered with the composite mixed titanium deoxid film layer of cobalt ruthenium, is covered with titanium deoxid film layer more outward at the composite mixed titanium deoxid film layer of cobalt ruthenium.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; Optoelectronic pole outermost layer is made up of titanium dioxide, is diminished gradually, be conducive to different-waveband light and absorb successively, thus fully expand the spectral response scope of material by outer energy gap inward, and the stable performance of optoelectronic pole; Single homogeneous phase metal ion or grade doping is greatly better than at one or more aspect of performances such as light absorption, photocatalysis, opto-electronic conversion.The present invention effectively can be applied in fields such as Solar use, opto-electronic conversion, photocatalysis degradation organic contaminants.Application number be 201210370552.2 invention a kind of preparation method of ruthenium dioxide combination electrode for energy storage is proposed, it is characterized in that comprising the steps: a) the ruthenic oxide material of different content to be mixed with binding agent, thickener, carbon and deionized water in shear mixing equipment, make the multiple slurry that ruthenic oxide content is different, viscosity is different; B) slurry minimum for ruthenic oxide content is coated on collector, drying forming; C) use step b) method coated with multiple layer slurry.The ruthenic oxide combination electrode that the present invention obtains is combined with collector more closely, has the feature such as high power capacity and long-life, can be widely used in national defence and the energy storage field such as civilian.Application number 201210003214.5 a kind of preparation method of ruthenium oxide electrode of super capacitor of disclosure of the invention, belong to the preparation method of electrode for capacitors; The inventive method be be coated on tantalum paper tinsel surface containing adding valve metal powder and nano hydrated ruthenium-oxide in ruthenium compound slurry, then the tantalum paper tinsel after drying is put into water vapour environment to carry out thermal decomposition and prepare amorphous hydrated ruthenic oxide negative electrode, therefore, it is possible to avoid ruthenic oxide dewater crystallization, thus improve ruthenium oxide coatings and tantalum paper tinsel bond strength, improve the electroded specific capacity of ruthenium-oxide.The capacitor electrode adopting the inventive method to prepare has advantage, energy density and the power density advantages of higher such as resistance to elevated temperatures is good, anti-vibration ability is strong; It is a kind of method preparing ultracapacitor.Above prior art, does not all solve the technical problem of " existing solid electrolyte Ta capacitor due to the capacity of negative electrode on the low side and be difficult to the solid electrolyte tantalum electrolytic capacitor of capacity of preparing large (more than 1mF) ".
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of conductive polymer ruthenium dioxide membrane electrode and preparation method thereof, by being combined into jumbo conductive solid polymer electrolyte tantalum capacitor with jumbo tantalum anode, the technical problem of " existing solid electrolyte Ta capacitor due to the capacity of negative electrode on the low side and be difficult to the solid electrolyte tantalum electrolytic capacitor of capacity of preparing large (more than 1mF) " can be solved.
The technical solution used in the present invention: described conductive polymer ruthenium dioxide 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 base material, powder ruthenium dioxide dispersion membrane electrode wherein.This conducting polymer materials conducting polymer and ultrafine ruthenium oxide powder end formed by polymerization or mechanical mixture, ultrafine ruthenium oxide powder end is dispersed in conducting polymer body, and its conductivity is high, and capacity is large.
The preparation method of described conductive polymer ruthenium dioxide membrane electrode is: first powder ruthenium dioxide joined in 3,4-ethylene dioxythiophene monomer solution and/or oxidizing agent solution, mix; Again the tantalum piece of having polished is immersed in 3,4-ethylene dioxythiophene monomer solution, make tantalum piece adsorption one deck 3,4-ethylene dioxythiophene monomer; Again the tantalum piece being stained with 3,4-ethylene dioxythiophene monomer is immersed in oxidizing agent solution, repeatedly carry out 5-20 time; Be polymerized at the temperature of 0 DEG C ~+40 DEG C, until the conduction that tantalum piece surface is formed containing powder ruthenium dioxide gathers 3,4-ethylene dioxythiophene film.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 conductive polymer ruthenium dioxide membrane electrode also can adopt with the following method: first powder ruthenium dioxide is added be polymerized in advance 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; Dry at normal temperatures, until tantalum piece surface is formed containing the poly-3,4-ethylene dioxythiophene film of powder ruthenium dioxide conduction.
Described jumbo conductive solid polymer electrolyte tantalum capacitor, comprise tantalum anode and the chip membrane electrode being positioned at tantalum anode surface, described chip membrane electrode adopts above-mentioned conductive polymer ruthenium dioxide membrane electrode.
Conductive polymer ruthenium dioxide membrane electrode of the present invention is a kind of conducting polymer and powder ruthenium dioxide composite film electrode of tantalum electrolytic capacitor, preparation method is simple, this membrane electrode can use in the scope of-55 DEG C ~+125 DEG C, can carry out unlimited discharge and recharge.The present invention utilizes the specific volume of ruthenic oxide material to increase the capacity of prepared membrane electrode, thus prepare jumbo chip membrane electrode, again by the jumbo tantalum anode of preparation, be combined into jumbo conductive solid polymer electrolyte tantalum capacitor with chip membrane electrode, thus the technical problem of " solid electrolyte Ta capacitor due to the capacity of negative electrode on the low side and be difficult to the solid electrolyte tantalum electrolytic capacitor of capacity of preparing large (more than 1mF) " to be solved in prior art well.
Accompanying drawing explanation
Fig. 1 is conductive polymer ruthenium dioxide membrane electrode generalized section;
Fig. 2 is conductive polymer ruthenium dioxide membrane electrode outline drawing.
Wherein: 1, poly-3,4-ethylene dioxythiophene; 2, powder ruthenium dioxide; 3, tantalum piece.
Embodiment
As shown in Figure 1 and Figure 2, described conductive polymer ruthenium dioxide membrane electrode, by 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 base material, powder ruthenium dioxide dispersion conducting polymer materials wherein, its conductivity is high, capacity is large, and is formed at tantalum piece 3 surface of tantalum capacitor, thus prepares jumbo chip membrane electrode.Again by the jumbo tantalum anode of preparation, be combined into jumbo conductive solid polymer electrolyte tantalum capacitor with chip membrane electrode.
The preparation method of conductive polymer ruthenium dioxide membrane electrode is further illustrated below in conjunction with following three specific embodiments.
Embodiment one:
Powder ruthenium dioxide 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; Again the tantalum piece being stained with monomer is immersed in oxidizing agent solution, repeatedly carry out 5-20 time; Be polymerized at the temperature of 0 DEG C ~+40 DEG C, until the conduction that tantalum piece surface is formed containing powder ruthenium dioxide gathers 3,4-ethylene dioxythiophene film.
Embodiment two:
Powder ruthenium dioxide is joined in the solution of oxidant toluenesulfonic acid iron, mix; Again the tantalum piece of polishing is first immersed in 3,4-ethylene dioxythiophene monomer solution, until tantalum piece surface is formed containing 3,4-ethylene dioxythiophene monomer film; Then tantalum piece is immersed in oxidizing agent solution, 5-20 time repeatedly; Be polymerized at the temperature of 0 DEG C ~+40 DEG C, until the conduction that tantalum piece surface is formed containing powder ruthenium dioxide gathers 3,4-ethylene dioxythiophene film.
Embodiment three:
Powder ruthenium dioxide is added in the solution of the poly-3,4-ethylene dioxythiophene be polymerized in advance, mix; Again the tantalum piece of having polished is immersed in this solution, 5-20 time repeatedly; Dry at normal temperatures, until tantalum piece surface is formed containing the poly-3,4-ethylene dioxythiophene film of powder ruthenium dioxide conduction.
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 amendment done, equivalent replacement, improvement etc., be all included within protection scope of the present invention.
Claims (5)
1. a preparation method for conductive polymer ruthenium dioxide membrane electrode, is characterized in that, first powder ruthenium dioxide is joined in 3,4-ethylene dioxythiophene monomer solution and/or oxidizing agent solution, mixes; Again the tantalum piece of having polished is immersed in 3,4-ethylene dioxythiophene monomer solution, make tantalum piece adsorption one deck 3,4-ethylene dioxythiophene monomer; Again the tantalum piece being stained with 3,4-ethylene dioxythiophene monomer is immersed in oxidizing agent solution, repeatedly carry out 5-20 time; Be polymerized at the temperature of 0 DEG C ~+40 DEG C, until the conduction that tantalum piece surface is formed containing powder ruthenium dioxide gathers 3,4-ethylene dioxythiophene film.
2. the preparation method of conductive polymer ruthenium dioxide membrane electrode according to claim 1, 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.
3. the preparation method of conductive polymer ruthenium dioxide membrane electrode according to claim 1, is characterized in that, described oxidizing agent solution is oxidant toluenesulfonic acid ferrous solution.
4. a preparation method for conductive polymer ruthenium dioxide membrane electrode, is characterized in that, first powder ruthenium dioxide is added in the poly-3,4-ethylene dioxythiophene solution be polymerized in advance, mixes; Again the tantalum piece of having polished is immersed in this solution, 5-20 time repeatedly; Dry at normal temperatures, until tantalum piece surface is formed containing the poly-3,4-ethylene dioxythiophene film of powder ruthenium dioxide conduction.
5. the preparation method of conductive polymer ruthenium dioxide membrane electrode according to claim 4, 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.
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| 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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| Microwave-assisted synthesis of organic–inorganic;Li Chen ， Changzhou Yuan ，Bo Gao 等;《J Solid State Electrochem》;20090114(第13期);第1925-1933页 * |
| 二氧化钌薄膜电极的制备及其性能研究;张莉，邹积岩，宋金岩;《仪器仪表学报》;20061230;第27卷(第6期);第930页引言部分左栏第3行-右栏的第8行 * |
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