CN100576389C - The preparation method of the conductive polymer cathode material of solid sheet type aluminum electrolytic capacitor - Google Patents
The preparation method of the conductive polymer cathode material of solid sheet type aluminum electrolytic capacitor Download PDFInfo
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- CN100576389C CN100576389C CN200610045344A CN200610045344A CN100576389C CN 100576389 C CN100576389 C CN 100576389C CN 200610045344 A CN200610045344 A CN 200610045344A CN 200610045344 A CN200610045344 A CN 200610045344A CN 100576389 C CN100576389 C CN 100576389C
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- paratoluenesulfonic acid
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Abstract
The present invention relates to a kind of preparation method of conductive polymer cathode material of solid sheet type aluminum electrolytic capacitor, with 3,4-ethene dioxythiophene (EDT) is as the monomer of conductive polymer cathode material, adopt repeatedly the chemical oxidization method preparation, comprise that inner layer film is made and outer membrane is made two main technique.This technology not only simply is convenient to implement, and manufactured goods conductance height; Have better thermal stability and moisture resistance.
Description
Technical field
The present invention relates to a kind of preparation method of conductive polymer cathode material of solid sheet type aluminum electrolytic capacitor.
Background technology
Solid sheet type aluminum electrolytic capacitor has overcome the drawback that the conventional aluminum electrolytic capacitor uses liquid electrolyte, reduced capacitor equivalent series resistance (ESR), improved capacitance, enlarged the frequency range of using.Conducting high polymers thing material (or conductive plastics) as the high-tech material of a new generation, since being synthesized the seventies, has been the popular object of academia and industrial quarters research and development in decades always.With the solid state cathode material of conducting high polymers thing as aluminium electrolytic capacitor, made aluminium electrolytic capacitor in high stability, long-life, and enlarge aspect such as range of application quantum jump arranged.As the conducting high polymers thing, the conductance of polypyrrole (PPY) can reach 20S/cm, and is higher 10 times than TCNQ, higher more than 100 times than the conductance of the liquid electrolyte in the conventional aluminum electrolytic capacitor.Baytron company is the conductive plastics of new generation of invention in the recent period, and 3,4-polyethylene dioxythiophene (PEDT), conductance can reach 100S/cm, and heat decomposition temperature height (＞245 ℃).Conducting polymer is applied to also have in the solid sheet type aluminum electrolytic capacitor characteristic of " self-healing " as cathode material, and can not burn.
Summary of the invention
The present invention seeks to provide a kind of preparation method of conductive polymer cathode material of solid sheet type aluminum electrolytic capacitor, this technology not only simply is convenient to implement, and manufactured goods conductance height: have better thermal stability and moisture resistance.
The preparation method of the conductive polymer cathode material of solid sheet type aluminum electrolytic capacitor of the present invention comprises that inner layer film is made and outer membrane is made two main technique, and concrete steps are as follows:
1), inner layer film is made
(a) aluminium anodes after the anodization being immersed concentration is (in the ethanol of 10～46wt%) EDT, n-butanol or the isopropyl alcohol monomer solution, to take out oven dry; Aluminium anodes after the described anodization is the aluminium anodes of the nonconducting deielectric-coating Al2O3 of one deck for the surface;
(b) aluminium anodes after will drying immerses the toluene sulfonic acide molten iron solution I that contains anthraquinone-2-sodium, paratoluenesulfonic acid sodium salt or neopelex, perhaps contain among the ammonium persulfate aqueous solution I of anthraquinone-2-sodium, paratoluenesulfonic acid sodium salt or neopelex, take out oven dry; Wherein the content of anthraquinone-2-sodium, paratoluenesulfonic acid sodium salt or neopelex is 0.02～0.15mol/L, and the content of toluene sulfonic acide iron or ammonium persulfate is 0.5～1.5mol/L;
(c) place air to cool off;
(d) repeat (a) (c) step 3～15 times;
2), outer membrane is made
(e) will finish the aluminium anodes immersion concentration of (d) step for (in the ethanol of 10～46wt%) EDT, n-butanol or the isopropyl alcohol monomer solution, taking out oven dry;
(f) aluminium anodes after will drying immerses the toluene sulfonic acide molten iron solution II that contains anthraquinone-2-sodium, paratoluenesulfonic acid sodium salt or neopelex, perhaps contain among the ammonium persulfate aqueous solution II of anthraquinone-2-sodium, paratoluenesulfonic acid sodium salt or neopelex, take out oven dry; Wherein the content of anthraquinone-2-sodium, paratoluenesulfonic acid sodium salt or neopelex is 0.05～0.5mol/L, and the content of toluene sulfonic acide iron or ammonium persulfate is 2.0～5.0mol/L;
(g) place air to cool off;
(h) repeat (e) → (g) step 5-20 time;
3), clean
(i) will finish the aluminium anodes washed with de-ionized water of (h) step; The ethanol of above-mentioned EDT, n-butanol or isopropyl alcohol monomer solution concentration are 24.35wt%.Solution I is preferably the 1.0mol/L toluene sulfonic acide molten iron solution that contains 0.1mol/L anthraquinone-2-sodium, paratoluenesulfonic acid sodium salt or neopelex, and perhaps 0.1mol/L contains the 1.0mol/L ammonium persulfate aqueous solution of anthraquinone-2-sodium, paratoluenesulfonic acid sodium salt or neopelex.Solution II is preferably the 3.5mol/L toluene sulfonic acide molten iron solution that contains 0.2mol/L anthraquinone-2-sodium, paratoluenesulfonic acid sodium salt or neopelex, perhaps contains the 3.5mol/L ammonium persulfate aqueous solution of 0.2mol/L anthraquinone-2-sodium, paratoluenesulfonic acid sodium salt or neopelex.
As the cathode material of solid sheet type aluminum electrolytic capacitor, the PEDT conducting polymer film needs by " plating " surface at aluminium anodes.Because the surface of aluminium anodes nonconducting deielectric-coating Al that is one deck
2O
3So in fact " plating " film is meant that conducting polymer film is by " plating " Al on aluminium anodes
2O
3The surface.
In technological process of the present invention, aluminium anodes immerses monomer solution earlier, reenters in the oxidant, takes out the reaction film forming, and repeats to obtain required thickness.Wherein cleaning step is to eliminate reactant and the product that remains in conducting polymer film and the aluminium anodes.The PEDT conductive polymer cathode material that this technical matters forms makes solid sheet type aluminum electrolytic capacitor have following good performance:
1, anti-mechanical stress and thermal stress resistance height;
2, form thin and the uniform PEDT film of thickness, greatly reduced the ESR of capacitor;
3, the PEDT film has improved the chemistry and the thermal stability of capacitor not with the impurity of Cl and Fe.
Description of drawings
Fig. 1 is the manufacture craft flow chart of the conducting polymer negative electrode of solid sheet type aluminum electrolytic capacitor.
Embodiment
Aluminium anodes after the anodization was immersed in ethanol, n-butanol or the aqueous isopropanol that EDT concentration is 24.35wt% 5 seconds, take out oven dry; Immersed again in the 1.0mol/L toluene sulfonic acide iron of 0.1mol/L anthraquinone-2-sodium, paratoluenesulfonic acid sodium salt or neopelex or the ammonium persulfate aqueous solution 5 seconds, and took out oven dry, and place air cooling 2 minutes; Repeat above-mentioned steps 5 times.
The aluminium chip of finishing above-mentioned steps was immersed in ethanol, n-butanol or the aqueous isopropanol that EDT concentration is 24.35wt% 5 seconds, take out oven dry; Immerse the 3.5mol/L toluene sulfonic acide iron of 0.2mol/L anthraquinone-2-sodium, paratoluenesulfonic acid sodium salt or neopelex or ammonium persulfate aqueous solution again 5 seconds, and took out oven dry, and place air cooling 2 minutes; Repeat above-mentioned steps 9 times.
Use washed with de-ionized water aluminium chip at last, promptly finish whole manufacture craft.
Make 5 capacitor elements with present embodiment, end properties is as shown in table 1
| Capacity (μ F) | Loss | ESR(mΩ) | Leakage current (μ A) | ESR after the Reflow Soldering (m Ω) |
| 9.0 | 0.009 | 45.8 | 0.22 | 55.0 |
| 9.2 | 0.006 | 43.0 | 0.23 | 53.9 |
| 8.9 | 0.007 | 44.6 | 0.20 | 54.6 |
| 9.1 | 0.007 | 45.1 | 0.22 | 55.2 |
| 9.5 | 0.008 | 45.9 | 0.26 | 51.7 |
The present invention is novel, and is reasonable in design, manufactured goods conductance height; Have better thermal stability and moisture resistance, have bigger application value.
Claims (4)
1, a kind of preparation method of conductive polymer cathode material of solid sheet type aluminum electrolytic capacitor is characterized in that: comprise that inner layer film makes sharp outer membrane and make two main technique, concrete steps are as follows
1), inner layer film is made
(a) aluminium anodes after the anodization being immersed concentration is 10～46wt%3, in the ethanol of 4-ethene dioxythiophene, n-butanol or the isopropyl alcohol monomer solution, takes out oven dry; Aluminium anodes after the described anodization is that the surface is the nonconducting deielectric-coating Al of one deck
2O
3Aluminium anodes;
(b) aluminium anodes after will drying immerses the toluene sulfonic acide molten iron solution I that contains anthraquinone-2-sodium, paratoluenesulfonic acid sodium salt or neopelex, perhaps contain among the ammonium persulfate aqueous solution I of anthraquinone-2-sodium, paratoluenesulfonic acid sodium salt or neopelex, take out oven dry; Wherein the content of anthraquinone-2-sodium, paratoluenesulfonic acid sodium salt or neopelex is 0.02～0.15mol/L, and the content of toluene sulfonic acide iron or ammonium persulfate is 0.5～1.5mol/L;
(c) place air to cool off;
(d) repeat (a) (c) step 3～15 times;
2), outer membrane is made
(e) to immerse concentration be 10～46wt%3 to the aluminium anodes that will finish (d) step, in the ethanol of 4-ethene dioxythiophene, n-butanol or the isopropyl alcohol monomer solution, takes out oven dry;
(f) aluminium anodes after will drying immerses the toluene sulfonic acide molten iron solution II that contains anthraquinone-2-sodium, paratoluenesulfonic acid sodium salt or neopelex, perhaps contain among the ammonium persulfate aqueous solution II of anthraquinone-2-sodium, paratoluenesulfonic acid sodium salt or neopelex, take out oven dry; Wherein the content of anthraquinone-2-sodium, paratoluenesulfonic acid sodium salt or neopelex is 0.05～0.5mol/L, and the content of toluene sulfonic acide iron or ammonium persulfate is 2.0～5.0mol/L;
(g) place air to cool off;
(h) repeat (e) → (g) step 5-20 time;
3), clean
(i) will finish the aluminium anodes washed with de-ionized water of (h) step.
2, the preparation method of the conductive polymer cathode material of solid sheet type aluminum electrolytic capacitor according to claim 1 is characterized in that: 3, and the ethanol of 4-ethene dioxythiophene, n-butanol or isopropyl alcohol monomer solution concentration are 24.35wt%.
3, the preparation method of the conductive polymer cathode material of solid sheet type aluminum electrolytic capacitor according to claim 1, it is characterized in that: solution I is the 1.0mol/L toluene sulfonic acide molten iron solution that contains 0.1mol/L anthraquinone-2-sodium, paratoluenesulfonic acid sodium salt or neopelex, and perhaps 0.1mol/L contains the 1.0mol/L ammonium persulfate aqueous solution of anthraquinone-2-sodium, paratoluenesulfonic acid sodium salt or neopelex.
4, the preparation method of the conductive polymer cathode material of solid sheet type aluminum electrolytic capacitor according to claim 1, it is characterized in that: solution II is the 3.5mol/L toluene sulfonic acide molten iron solution that contains 0.2mol/L anthraquinone-2-sodium, paratoluenesulfonic acid sodium salt or neopelex, perhaps contains the 3.5mol/L ammonium persulfate aqueous solution of 0.2mol/L anthraquinone-2-sodium, paratoluenesulfonic acid sodium salt or neopelex.
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| CN101871115A (en) * | 2010-05-31 | 2010-10-27 | 福建国光电子科技股份有限公司 | Electrolyte used for treating aluminium foil in aluminium electrolytic capacitor |
| CN101866750A (en) * | 2010-06-23 | 2010-10-20 | 福建国光电子科技股份有限公司 | Electrochemical polymerization process for forming solid electrolyte layer on solid electrolytic capacitor |
| CN101866748A (en) * | 2010-06-23 | 2010-10-20 | 福建国光电子科技股份有限公司 | Chemical polymerization process for forming solid electrolyte layer on solid electrolytic capacitor |
| CN101894672A (en) * | 2010-06-23 | 2010-11-24 | 福建国光电子科技股份有限公司 | Chemical polymerization process for forming solid electrolyte layer by solid electrolytic capacitor |
| CN102543491B (en) * | 2012-02-29 | 2013-12-04 | 万星光电子(东莞)有限公司 | Manufacturing method for laminated solid aluminium electrolytic capacitor |
| CN107039184B (en) * | 2017-04-01 | 2019-10-22 | 中南大学 | A kind of solid-state aluminum electrolytic capacitor and preparation method thereof |
| CN113990665B (en) * | 2020-07-27 | 2023-05-26 | 深圳市柏瑞凯电子科技股份有限公司 | Manufacturing method of conductive polymer cathode material of laminated solid aluminum electrolytic capacitor |
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| 导电聚合物BAYTRON及其在固体电解电容器上的应用. 陈湘宁.电子元件与材料，第19卷第3期. 2000 |
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