CN104059226A - Electrochemical polymerization process for preparing polypyrrole - Google Patents
Electrochemical polymerization process for preparing polypyrrole Download PDFInfo
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- CN104059226A CN104059226A CN201410292456.XA CN201410292456A CN104059226A CN 104059226 A CN104059226 A CN 104059226A CN 201410292456 A CN201410292456 A CN 201410292456A CN 104059226 A CN104059226 A CN 104059226A
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Abstract
The invention provides an electrochemical polymerization process for preparing polypyrrole. In the electrochemical polymerization process, the PH value of a polymerization solution is controlled within the range of 3.0-6.0 by using a PH value regulator containing supporting electrolyte; meanwhile, the electrochemical polymerization temperature is limited within the range of 0-30 DEG C, and the electrochemical polymerization time is limited within the range of 60-200min. By using the process provided by the invention, the leak current property of a prepared solid polymer aluminum electrolytic capacitor and characteristics of the prepared solid polymer aluminum electrolytic capacitor under high temperature and high humidity environments are more excellent.
Description
Technical field
The present invention relates to a kind of electrochemical polymerization process of preparing polypyrrole of solid electrolytic capacitor.
Background technology
We know, under high temperature and super-humid conditions, work long hours, and solid capacitor easily causes performance degradation, cause capacity to reduce, and equivalent series resistance (ESR) increases, and leakage current value increases.In order to address the above problem, in way in the past, have, by increasing the wall thickness of potting resin of pin one side of electrical condenser, extend the distance between potting resin outer end and capacitor cathode and anode; Or carry out coated with resins again at electrical condenser pin with the gap that contacts of potting resin, delay entering of airborne oxygen and steam, thereby the capacitor performance of improvement under hot and humid condition is deteriorated.
The problem existing in above-mentioned way is in the past, by increasing the method for potting resin wall thickness, will cause the physical dimension of electrical condenser to increase, and result causes being difficult to realize miniaturization, can not meet especially the demand of current miniaturization of electronic products.And by the way that contacts gap and carry out again coated with resins at electrical condenser pin and potting resin, on equipment, be difficult to realize automatization, and be unfavorable for the production in enormous quantities technique of industrialization,, capacitor product outward appearance is also had a certain impact meanwhile.
Summary of the invention
The technical problem to be solved in the present invention, comprises the not good problem of memory property under the bigger than normal and hot and humid environment of the leakage current of solid polymer aluminium electrolutic capacitor that solves.
The present invention is achieved in that provides a kind of electrochemical polymerization process of preparing polypyrrole, in electrochemical polymerization process, use and the supporting electrolyte pH value conditioning agent that is same material by the pH value scope control of polymeric solution between 3.0～6.0; Meanwhile, by electrochemical polymerization temperature limitation between 0-30 DEG C, by electrochemical polymerization time limitation between 60-200min.
Further, the mode that described pH value conditioning agent adopts timing to add is added in polymeric solution.
Further, described timing is added to every 5-10min and adds once.
Further, described electrochemical polymerization solution comprises Py and supporting electrolyte.
Further, the supporting electrolyte of described electrochemical polymerization solution comprises any in p-methyl benzenesulfonic acid and salt, Witco 1298 Soft Acid and salt thereof, dodecyl sodium sulfonate and salt thereof, camphorsulfonic acid and salt thereof, Phenylsulfonic acid and salt thereof, naphthene sulfonic acid and salt thereof, dibutyl naphthalene sulfonic acid and salt thereof, phenol sulfonic acid and salt, sulphosalicylic acid and salt thereof, sulfosalicylic acid and salt thereof, naphthalene disulfonic acid and salt thereof, benzene disulfonic acid and salt thereof, anthraquinone disulfonic acid and salt thereof.
Further, the current density of described electrochemical polymerization is 3mA/cm
2～10mA/cm
2between.
Tool of the present invention has the following advantages: the present invention, without increasing potting resin wall thickness, without the physical dimension that increases electrical condenser, is conducive to miniaturization development; The present invention, without increasing new equipment and Automation of Manufacturing Process, is conducive to the production in enormous quantities of industrialization; Under leakage current characteristic and hot and humid environment in end properties of the present invention, the characteristic of (85 DEG C, 85%RH, after 1000h) product is obviously better; Features simple and practical process of the present invention, has significant economic benefit.
Embodiment
Embodiment 1:
In electrochemical polymerization operation, the aluminium foil cathode portion that surface is formed to pre-conductive layer is connected as anode with additional electrodes, in the mixed solution containing the Py of 0.45M and the p-methyl benzenesulfonic acid of 0.35M and salt thereof, carry out constant-current electrolysis taking stainless steel electrode as negative electrode, controlling polymeric solution temperature is 0 DEG C, and current density is 3mA/cm
2, the time is 60 minutes, then cleaning, drying; Wherein, realizing control solution pH value by timing every the mixed solution of 5min interpolation p-methyl benzenesulfonic acid and salt thereof is 3.0.
Embodiment 2:
Except supporting electrolyte is Witco 1298 Soft Acid and salt thereof, polymeric solution temperature is 5 DEG C, and current density is 7mA/cm
2, the time is 75 minutes, and realizing control solution pH value by timing every the mixed solution of 8min interpolation Witco 1298 Soft Acid and salt thereof is outside 4.0, and all the other are with embodiment 1.
Embodiment 3:
Except supporting electrolyte is dodecyl sodium sulfonate and salt thereof, polymeric solution temperature is 30 DEG C, and current density is 10mA/cm
2, the time is 90 minutes, and realizing control solution pH value by timing every the mixed solution of 10min interpolation dodecyl sodium sulfonate and salt thereof is outside 5.0, and all the other are with embodiment 1.
Embodiment 4:
Except supporting electrolyte is naphthene sulfonic acid and salt thereof, polymeric solution temperature is 15 DEG C, and current density is 6mA/cm
2, the time is 75 minutes, and realizing control solution pH value by timing every the mixed solution of 5min interpolation naphthene sulfonic acid and salt thereof is outside 4.5, and all the other are with embodiment 1.
Embodiment 5:
Except supporting electrolyte is camphorsulfonic acid and salt thereof, polymeric solution temperature is 20 DEG C, and current density is 5mA/cm
2, the time is 120 minutes, and realizing control solution pH value by timing every the mixed solution of 8min interpolation camphorsulfonic acid and salt thereof is outside 6.0, and all the other are with embodiment 1.
Embodiment 6:
Except supporting electrolyte is Phenylsulfonic acid and salt thereof, polymeric solution temperature is 15 DEG C, and current density is 5mA/cm
2, the time is 150 minutes, and realizing control solution pH value by timing every the mixed solution of 5min interpolation Phenylsulfonic acid and salt thereof is outside 3.0, and all the other are with embodiment 1.
Embodiment 7:
Except supporting electrolyte is dibutyl naphthalene sulfonic acid and salt thereof, polymeric solution temperature is 25 DEG C, and current density is 7mA/cm
2, the time is 110 minutes, and realizing control solution pH value by timing every the mixed solution of 5min interpolation dibutyl naphthalene sulfonic acid and salt thereof is outside 3.5, and all the other are with embodiment 1.
Embodiment 8:
Except supporting electrolyte is phenol sulfonic acid and salt thereof, polymeric solution temperature is 10 DEG C, and current density is 7mA/cm
2, the time is 160 minutes, and realizing control solution pH value by timing every the mixed solution of 8min interpolation phenol sulfonic acid and salt thereof is outside 4.5, and all the other are with embodiment 1.
Embodiment 9:
Except supporting electrolyte is sulphosalicylic acid and salt thereof, polymeric solution temperature is 5 DEG C, and current density is 8mA/cm
2, the time is 180 minutes, and realizing control solution pH value by timing every the mixed solution of 10min interpolation sulphosalicylic acid and salt thereof is outside 5.5, and all the other are with embodiment 1.
Embodiment 10:
Except supporting electrolyte is sulfosalicylic acid and salt thereof, polymeric solution temperature is 5 DEG C, and current density is 8mA/cm
2, the time is 120 minutes, and realizing control solution pH value by timing every the mixed solution of 10min interpolation sulfosalicylic acid and salt thereof is outside 4.5, and all the other are with embodiment 1.
Embodiment 11:
Except supporting electrolyte is naphthalene disulfonic acid and salt thereof, polymeric solution temperature is 15 DEG C, and current density is 5mA/cm
2, the time is 150 minutes, and realizing control solution pH value by timing every the mixed solution of 8min interpolation naphthalene disulfonic acid and salt thereof is outside 4.0, and all the other are with embodiment 1.
Embodiment 12:
Except supporting electrolyte is benzene disulfonic acid and salt thereof, polymeric solution temperature is 10 DEG C, and current density is 5mA/cm
2, the time is 150 minutes, and realizing control solution pH value by timing every the mixed solution of 8min interpolation benzene disulfonic acid and salt thereof is outside 4.5, and all the other are with embodiment 1.
Embodiment 13:
Except supporting electrolyte is anthraquinone disulfonic acid and salt thereof, polymeric solution temperature is 20 DEG C, and current density is 3mA/cm
2, the time is 200 minutes, and realizing control solution pH value by timing every the mixed solution of 5min interpolation anthraquinone disulfonic acid and salt thereof is outside 6.0, and all the other are with embodiment 1.
Comparative example one:
In electrochemical polymerization operation, the aluminium foil cathode portion that surface is formed to pre-conductive layer is connected as anode with additional electrodes, in the mixed solution containing the Py of 0.2M and the toluenesulfonate of 0.4M, carry out constant-current electrolysis taking stainless steel electrode as negative electrode, controlling solution temperature is 35 DEG C, and current density is 6mA/cm
2, the time is 30 minutes, then cleaning, drying; Wherein, realizing control solution pH value by timing every the mixed solution of 5min interpolation p-methyl benzenesulfonic acid and salt thereof is 2.0.
Comparative example two:
In electrochemical polymerization operation, the aluminium foil cathode portion that surface is formed to pre-conductive layer is connected as anode with additional electrodes, in the mixed solution containing the Py of 0.45M and the naphthalenesulfonate of 0.35M, carry out constant-current electrolysis taking stainless steel electrode as negative electrode, controlling solution temperature is 45 DEG C, and current density is 12mA/cm
2, the time is 10 minutes, then cleaning, drying; Wherein, realizing control solution pH value by timing every the mixed solution of 10min interpolation naphthene sulfonic acid and salt thereof is 6.5.
Comparative example three:
In electrochemical polymerization operation, the aluminium foil cathode portion that surface is formed to pre-conductive layer is connected as anode with additional electrodes, in the mixed solution containing the Py of 0.5M and the dodecylbenzene sulfonate of 0.5M, carry out constant-current electrolysis taking stainless steel electrode as negative electrode, controlling solution temperature is 40 DEG C, and current density is 1mA/cm
2, the time is 50 minutes, then cleaning, drying; Wherein, realizing control solution pH value by timing every the mixed solution of 8min interpolation Witco 1298 Soft Acid and salt thereof is 7.5.
After the electrochemical polymerization process of above-described embodiment and comparative example completes, to forming cathode portion coated graphite and the silver slurry successively of electroconductive polymer layer, by anode and negative electrode are set, form capacitor body; Finally with epoxy resin by capacitor body molded packages.
Effect comparison
By upper Biao Ke get, the embodiment of the present invention is compared with comparative example, and the characteristic under leakage current characteristic and the hot and humid environment of the solid polymer aluminium electrolutic capacitor preparing is better.
Although more than described the specific embodiment of the present invention; but being familiar with those skilled in the art is to be understood that; our described specific embodiment is illustrative; instead of for the restriction to scope of the present invention; those of ordinary skill in the art are in equivalent modification and the variation done according to spirit of the present invention, all should be encompassed in the scope that claim of the present invention protects.
Claims (6)
1. an electrochemical polymerization process of preparing polypyrrole, is characterized in that: in electrochemical polymerization process, use contain supporting electrolyte pH value conditioning agent by the pH value scope control of electrochemical polymerization solution between 3.0～6.0; Meanwhile, by electrochemical polymerization temperature limitation between 0-30 DEG C, by electrochemical polymerization time limitation between 60-200min.
2. the electrochemical polymerization process of preparing polypyrrole according to claim 1, is characterized in that: the mode that described pH value conditioning agent adopts timing to add is added in polymeric solution.
3. the electrochemical polymerization process of preparing polypyrrole according to claim 2, is characterized in that: described timing is added to every 5-10min to be added once.
4. according to the electrochemical polymerization process of preparing polypyrrole described in claims 1 to 3 any one, it is characterized in that: described electrochemical polymerization solution comprises pyrroles (Py) and supporting electrolyte.
5. the electrochemical polymerization process of preparing polypyrrole according to claim 4, is characterized in that: supporting electrolyte comprises any in p-methyl benzenesulfonic acid and salt, Witco 1298 Soft Acid and salt thereof, dodecyl sodium sulfonate and salt thereof, camphorsulfonic acid and salt thereof, Phenylsulfonic acid and salt thereof, naphthene sulfonic acid and salt thereof, dibutyl naphthalene sulfonic acid and salt thereof, phenol sulfonic acid and salt, sulphosalicylic acid and salt thereof, sulfosalicylic acid and salt thereof, naphthalene disulfonic acid and salt thereof, benzene disulfonic acid and salt thereof, anthraquinone disulfonic acid and salt thereof.
6. the electrochemical polymerization process of preparing polypyrrole according to claim 4, is characterized in that: the current density of described electrochemical polymerization is 3mA/cm
2～10mA/cm
2between.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410292456.XA CN104059226A (en) | 2014-06-25 | 2014-06-25 | Electrochemical polymerization process for preparing polypyrrole |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108231434A (en) * | 2017-12-27 | 2018-06-29 | 益阳艾华富贤电子有限公司 | solid capacitor preparation method |
| CN112825287A (en) * | 2019-11-20 | 2021-05-21 | 三星电机株式会社 | Solid electrolytic capacitor and method for manufacturing the same |
| CN113444365A (en) * | 2021-07-13 | 2021-09-28 | 浙江科技学院 | Hybrid doped polypyrrole paper-based flexible electrode material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4547270A (en) * | 1983-07-27 | 1985-10-15 | Basf Aktiengesellschaft | Electrochemical polymerization of pyrroles, an anode for carrying this out, and products obtained by this procedure |
| WO2004102629A2 (en) * | 2003-05-08 | 2004-11-25 | Northeastern University | Method for synthesizing conducting polymers from neat monomer solutions |
| CN1649053A (en) * | 2005-02-05 | 2005-08-03 | 西安交通大学 | Method for producing solid sheet type 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 |
-
2014
- 2014-06-25 CN CN201410292456.XA patent/CN104059226A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4547270A (en) * | 1983-07-27 | 1985-10-15 | Basf Aktiengesellschaft | Electrochemical polymerization of pyrroles, an anode for carrying this out, and products obtained by this procedure |
| WO2004102629A2 (en) * | 2003-05-08 | 2004-11-25 | Northeastern University | Method for synthesizing conducting polymers from neat monomer solutions |
| CN1649053A (en) * | 2005-02-05 | 2005-08-03 | 西安交通大学 | Method for producing solid sheet type 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 |
Non-Patent Citations (1)
| Title |
|---|
| 陈远强: "电化学聚合电量对聚吡咯铝电容器性能影响", 《福建工程学院学报》, vol. 11, no. 3, 19 July 2013 (2013-07-19) * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108231434A (en) * | 2017-12-27 | 2018-06-29 | 益阳艾华富贤电子有限公司 | solid capacitor preparation method |
| CN108231434B (en) * | 2017-12-27 | 2021-10-08 | 益阳艾华富贤电子有限公司 | Method for preparing solid capacitor |
| CN112825287A (en) * | 2019-11-20 | 2021-05-21 | 三星电机株式会社 | Solid electrolytic capacitor and method for manufacturing the same |
| CN113444365A (en) * | 2021-07-13 | 2021-09-28 | 浙江科技学院 | Hybrid doped polypyrrole paper-based flexible electrode material and preparation method thereof |
| CN113444365B (en) * | 2021-07-13 | 2022-05-31 | 浙江科技学院 | Hybrid doped polypyrrole paper-based flexible electrode material and preparation method thereof |
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