WO2008042239A2 - Solid electrolytic capacitor and method of manufacturing the same - Google Patents
Solid electrolytic capacitor and method of manufacturing the same Download PDFInfo
- Publication number
- WO2008042239A2 WO2008042239A2 PCT/US2007/020899 US2007020899W WO2008042239A2 WO 2008042239 A2 WO2008042239 A2 WO 2008042239A2 US 2007020899 W US2007020899 W US 2007020899W WO 2008042239 A2 WO2008042239 A2 WO 2008042239A2
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- WO
- WIPO (PCT)
- Prior art keywords
- electrolytic capacitor
- polymerizable monomer
- solid electrolytic
- lewis base
- oxidant
- Prior art date
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/0029—Processes of manufacture
- H01G9/0036—Formation of the solid electrolyte layer
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
- H01G9/025—Solid electrolytes
- H01G9/028—Organic semiconducting electrolytes, e.g. TCNQ
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/15—Solid electrolytic capacitors
Definitions
- the present invention relates to a solid electrolytic capacitor and a method of manufacturing the same and, more particularly to a solid electrolytic capacitor with high voltage resistance and a method of manufacturing the same.
- an electrolytic capacitor utilizing metal with valve action such as aluminum
- metal with valve action used as an anode electrode is formed into an etching foil and the like to obtain a surface-roughened dielectric
- a downsized electrolytic capacitor with a large capacitance is provided.
- a solid electrolytic capacitor employing a solid electrolyte has good properties such as small size, large capacitance, and low equivalent series resistance. In addition to these properties, ease of making this product into chips and suitability for surface mounting is important. As a result, the solidelectrolytic capacitor is now indispensable for making electronic equipment smaller and more powerful.
- a solid electrolyte employed in a solid electrolytic capacitor.
- polyaniline, polythiophene, polyethylenedioxythiophene, and the like as the conductive polymers.
- PEDT Polyethylenedioxythiophene
- a capacitor employing PEDT uses chemical oxidative polymerization is made as follows. A capacitor element, formed by winding anode electrode foils and cathode electrode foils via separators, is impregnated with EDT (ethylenedioxythiophene) and an oxidant solution. It is then heated to form a PEDT polymer layer between both electrodes to result in the formation of a solid electrolytic capacitor (Japanese Unexamined Patent Publication No. 9(l997)-293639)
- Such a solid electrolytic capacitor as described above can be used for ⁇ vcar and inverter applications.
- withstand voltage is increased by forming a link composed of a compound having a vinyl group and a boric acid compound in a capacitor element (Japanese Unexamined Patent Publication No.. 2003-100560).
- one object of the invention which is proposed in order to resolve such problems of the prior art as described above, is to provide a solid electrolytic capacitor with high voltage resistance and a method of manufacturing the same.
- a solid electrolytic capacitor is produced by forming an electrolyte layer on an anode electrode formed of a valve metal oxide dielectric by a polymerization reaction in which an oxidative polymerizable monomer or an oxidative polymerizable monomer solution is mixed with an oxidant, wherein a Lewis base having a steric hindrance group with a nitrogen atom or a Lewis base having a hydrophilic radical with a nitrogen atom is adhered to a surface of the dielectric.
- the solid electrolytic capacitor is characterized in that the solid electrolytic capacitor is produced by forming an electrolyte layer on an anode electrode formed of a valve metal oxide dielectric by a polymerization reaction in which an oxidative polymerizable monomer or an oxidative polymerizable monomer solution is mixed with an oxidant, wherein a Lewis base, having a steric hindrance group with a nitrogen atom, or a Lewis base, having a hydrophilic radical with a nitrogen atom, is contained in the electrolyte layer.
- the anode electrode employed comprises aluminum or aluminum alloy.
- the solid electrolytic capacitor is produced from an anodic electrode foil formed of an aluminum oxide dielectric wound with a cathodic electrode foil via a separator to prepare a capacitor element.
- the capacitor element is then dipped in an electrolytic solution in which an oxidative polymerizable monomer or an oxidative polymerizable monomer solution is mixed with an oxidant.
- a polymerization reaction of polymers that conduct electricity then occurs in the capacitor element to form a solid electrolyte layer.
- the capacitor element is then stored in an outer package and an open-end of the package is sealed with a sealing member made of elastic rubber.
- an insulating resin band may be formed from a portion of an anodic electrode foil formed of aluminum oxide dielectric in order to distinguish between an extraction of the anodic electrode and the cathodic foil.
- the polymerizable monomer is then applied.
- the oxidant is applied to form the solid electrolyte layer.
- a graphite layer and a silver paste layer are then formed on the solid electrolyte layer sequentially in order to form an extraction of the cathodic electrode. Then, the extraction of the cathodic electrode and the external cathode terminal are connected with each other via the silver paste.
- the polymerizable monomer employed includes, for example, ethylenedioxythiophene (EDT), chemical oxidative polymerization of which forms polyethylenedioxythiophene (PEDT).
- EDT ethylenedioxythiophene
- PDT polyethylenedioxythiophene
- 3,4-ethylenedioxythiophene as a polymerizable monomer forms poly (3, 4-ethylenedioxythiophene) as the electrolyte layer.
- iron (III) p-toluenesulfonate dissolved in al-butanol solution is used as the oxidant.
- a method in which a polymerizable monomer and an oxidant are impregnated and applied to a capacitor element can be employed utilizing a method of dipping the capacitor element in a mixing solution of a monomer and an oxidant. Another method is dipping a capacitor element in a monomer solution before dipping it in an oxidant solution, or discharging the monomer solution to a capacitor element before discharging an oxidant solution etc.
- a Lewis base having a steric hindrance group with a nitrogen atom or a Lewis base having a hydrophilic radical with a nitrogen atom is adhered to a surface of the dielectric, or a Lewis base having a steric hindrance group with a nitrogen atom or a Lewis base having a hydrophilic radical with a nitrogen atom is contained in the electrolyte layer.
- the Lewis base employed in the present invention is a compound having at least one electron pair which is not shared or a lone pair.
- the Lewis base containing a nitrogen atom is a compound having a lone pair at the nitrogen atom, such as an amine, pyridine, imidazole or ammonia etc.
- the Lewis base having a steric hindrance group with a nitrogen atom comprises a substituted group near the lone pair of the nitrogen atom.
- the substituted groups constitute barriers to a reaction with the lone pair of the nitrogen and large cation.
- Such Lewis bases include 2,6-dimethylpyridine, 1,3-dimethyHsoquinoline, 2,4-dimethyHmidazole, 2, 6-dimethyl-pyrazine, 1, 8-Bis (dimethylamino) naphthalene (Proton-sponge), andAcridine.
- a proton which is a relatively small cation, is able to react with the nitrogen atom selectively.
- the acidity of the oxidant should be kept close to neutral. Attacks by the oxidant to the anode electrode are suppressed, improving the electrode voltage resistance property and also the voltage resistance of the electrolytic capacitor.
- Lewis bases having a plane symmetric substituted group
- Such Lewis bases include 3, 5-dimethylpyridine.
- the Lewis base is expected to have an electron density of the lone pair at the nitrogen atom increased due to the electron-releasing substituent. The reactivity with the proton is increased and accordingly, the acidity of the oxidant can be kept more basic. Attack by the oxidant to the anode electrode is suppressed. Thus, the electrode voltage resistance property and also the voltage resistance of the electrolytic capacitor are improved.
- the Lewis base comprises a reaction with a proton of the nitrogen atom, the acidity of the electrolyte can be kept close to neutral.
- an oxide film is covered due to the good binding activity of the hydrophilic radical to the dielectric oxide film so that a chemical attack by the oxidant to the anode electrode is prevented.
- the electrode voltage resistance property and also the voltage resistance of the electrolytic capacitor can be improved.
- ammonia or amine comprises a structure with an ammonia molecule.
- the NH3 group comprises a hydrogen binding to H2O having a high hydrophilic property in an aqueous solution, so that the effect can be provided.
- the preferred Lewis bases include a nitrogen atom, tertiary amine, such as tri-alkylamine, and aromatic amines, such as pyridine and imidazole.
- the Lewis base When adhering the Lewis base to a surface of the dielectric, it is used for a method in which the wound capacitor element is impregnated with the solution of the Lewis base, dried and adhered, or the other method in which an insulating resin band is formed before the solution of the Lewis base is applied and adhered to a certain portion of a surface of a dielectric. Accordingly, the acidity of the oxidant can be kept close to neutral. Attacks by the oxidant on the anode electrode are suppressed. Thus the electrode voltage resistance property and also the voltage resistance of the electrolytic capacitor are improved.
- the Lewis base when the Lewis base is contained in the electrolyte layer, it is used in the polymerization reaction liquid for polymerizing the resultant mixture.
- the following three methods can be used in the polymerization reaction.
- the polymerizable monomer or monomer solution is adhered to the anode electrode. Then an oxidant solution is adhered thereto, Subsequent heating causes the polymerization reaction to proceed.
- the polymerizable monomer or the monomer solution is adhered thereto. Subsequent heating causes the polymerization reaction to proceed.
- the resultant mixture is adhered to the anode electrode, and subsequent heating causes the polymerization reaction to proceed.
- the Lewis base is added to the monomer or the monomer solution and the oxidant solution.
- the Lewis base is added to the mixture.
- the plane symmetric dimethylpyridine has low vapor pressure and remains in a conductive polymer layer even after heating and oxidative polymerization.
- Fig. 1 is a graph showing voltage-current properties of an Al/PEDT capacitor with a conventionally formed voltage oxide of 40 V;
- Fig. 2 is a graph showing voltage-current properties after adding pyridine into the oxidant in PEDT polymerization of the capacitor of Fig. Il
- a solid electrolytic capacitor incorporates a Lewis base in an electrolyte layer for the formation of an electrolyte layer formed of polyethylenedioxythiophene (PEDT) on an anode electrode formed of aluminum by a polymerization reaction in which a polymerizable monomer or a monomer solution (EDT) is mixed with an oxidant.
- PEDT polyethylenedioxythiophene
- EDT monomer solution
- the Al/PEDT capacitor which will be used, has a very low equivalence series resistance (ESR) and high heat resistance that an Al electrolytic capacitor does not have, with significantly lower breakdown voltage than the voltage necessary for oxide formation and reduced leakage. It is suspected that low voltage resistance in the capacitor is caused by the dissolution or deterioration of an aluminum oxide film due to protons released from monomers during polymerization of Al oxide and the PEDT.
- ESR equivalence series resistance
- the /Vf ratio for the Al electrolytic capacitor is not more than 0.8, whereas the ratio for the Al/PEDT capacitor is less than 0.3. Accordingly, if the thickness of the oxide film can be reduced to almost as much as the Al electrolytic capacitor, and the V w /Vf ratio can be increased, a high voltage product can be produced whereby electricity can be saved for oxide formation. Moreover, the capacitance of the Al/PEDT can be increased dramatically so that the capacitance is doubled by simply replacing 100 V oxide with 50 V oxide.
- Ta/PEDT capacitor upon constantly charging current flows at a low electric field to a middle electric field, current increases exponentially near oxide film formation voltage, and finally breakdown voltage occurs.
- the breakdown voltage is close to the oxide film formation voltage, and its value is proportional to the oxide film formation voltage.
- Ta oxide is known as a very stable oxide, which is not dissolved or degraded by general acids, other than hydrofluoric acid.
- the Al/PEDT capacitor also has breakdown voltage close to the oxide film formation voltage, if the oxide film is not dissolved or degraded.
- the Al oxide is dissolved or degraded in a 60 degree centigrade oxidant solution, and further the Al oxide is dissolved in molten p-toluenesulfonic acid of a byproduct at 150 degree centigrade.
- An Al plate with a thickness of 0.5 mm was cut into a 0.64 cm diameter circle.
- the specimen was immersed in a 85 vol% H3PO4 vol% HNO3 mixture at 85 to 90 degree centigrade for 3 minutes, rinsed with water, rinsed with methanol, dried, and then stored in a desiccator. Just before anodic oxide formation, the specimen was immersed in 1 mol dm " 3 NaOH at room temperature for 3 minutes, immersed in 10 vol% HNO3 for 1 minute, rinsed with water, rinsed with methanol, and then dried.
- Anodic oxide was formed by applying a 0.83 mol dm' 3 ammonium adipate solution with a current density of up to 1 mAcm' 2 until the desired formation voltage was reached, followed by maintaining the voltage for 10 minutes. The formed specimen was then rinsed with water, rinsed with methanol to remove water, dried and then stored in the desiccator. (Masking and reformation)
- the specimens were masked with a polyimide tape with a thickness not more than 0.05 mm to define the sample area (diameter of 6 mm).
- the reformation of oxide was carried out in the same electrolyte solution as was used for the oxide film formation by keeping at prescribed formation voltage for 1 minute in order to repair any damage that might be caused during masking. (Monomer and oxidant)
- the monomer and oxidant employed were 3, 4-ethylenedioxythiophene (Baytron®MV2) and a 54 wt% iron (III) p-toluenesulfonate 1-butanol solution (Baytron ®C"B54), respectively.
- oxidant solutions containing pyridine with a molar ratio of 0.9, 2,6-dimethylpyridine, and 3,5-dimethylpyridine were used.
- the mixture was deposited on the Al oxide film to form a PEDT film.
- the specimen was spun at 600 rpm for 20 seconds to obtain a uniform film.
- spin coating was not employed since most of the mixture flew off a spinning disc due to its lower viscosity resulting from the fact that the addition of the Lewis base causes the polymerization rate to slow down. So the mixture was spread by tilting the specimen to cover the whole sample area.
- the polymer synthesis was carried out at 60 degree centigrade for 30 minutes, followed by 90 degree centigrade or 150 degree centigrade for 60 continuous minutes. Electrical contact between a Cu wire and the PEDT film was made with an silver paste. (Voltage-current curve measurement)
- V-i voltage -current
- PEDT was synthesized at different temperatures to investigate the effect of the polymerization temperature on voltage-current (V-i) curve.
- the melting point of p-toluenesulfonic acid is about 105 degree centigrade, so that the oxide film is not be damaged by molten p-toluenesulfonic acid if polymerization reaction is carried out below the melting point as diffusion of solid p-toluenesulfonic acid is likely to be limited.
- Fig. 1 shows the voltage-current curve of an Al/oxideWPEDT capacitor with polymer prepared at 90 degree centigrade and 150 degree centigrade in heat treatment twice.
- the voltage -current curve of a Ta/PEDT capacitor is also shown as a comparative.
- the charging current which was almost independent of the applied voltage corresponding to its capacitance, flew at low voltage (low electric field). Then the current exponentially increased, and finally a current jump occurred near oxide formation voltage.
- ramp voltage was applied from 0 V again on the sample after the current jump occurred, the current increased linearly with the applied voltage. That is, the current increased according to Ohm's law. This indicates that the sample was short circuited, i.e., breakdown occurred at the time of the current jump.
- Fig. 2 shows voltage -current curves of an Al/PEDT capacitor, where the PEDT was synthesized with and without pyridine in the oxidant.
- a voltage-current curve of a Ta/PEDT capacitor with a 40 V oxide film is also shown.
- the addition of pyridine somewhat reduces the current density. However, the value was much higher than that of the Ta/PEDT capacitor. This indicates that the addition of pyridine did not work for protecting an Al oxide film from a chemical attack by protons.
- Example 1 examines the effect on a voltage -current property in which 2, 6-dimethylpyridine is substituted for pyridine in the Comparative example described above.
- Example 2 examines the effect on a voltage-current property in which 3, 5-dimethylpyridine is substituted for the 2, 6-dimethylpyridine in Example 1 described above.
- Figs. 1 and 2 and Examples 1 and 2 show that in the Conventional example (Fig. l) and the Comparative example (Fig. 2), current flows together with voltage application, and in Examples 1 and 2, voltage increases even when no current flows, with the voltage resistance property enhanced. Furthermore, Example 1 shows better properties than Example 2. (Example 3)
- Example 3 examines the effect on a voltage-current property in which triisopropanolamine (formula 4) is substituted for 2, 6-dimethylpyridine in Example 1 described above and also tributylamine (formula 5) is used as Comparative example 2.
- the oxide formation voltage is 100 V.
- Tables 1 to 4 show voltage -current properties of an Al/PEDT capacitor with film formation voltage different from PEDT synthesized with oxidant with a hindered Lewis base and without a Lewis base, to which verification experiments were carried out.
- Table 1 shows a film formation voltage of 40 V.
- Table 2 shows a film formation voltage of 70 V.
- Table 3 and 4 show a capacitor with a film formation voltage of 100 V. It should be noted that Example (l) shows the addition of 2, 6-dimethylpyridine to the oxidant, that Example (2) shows the addition of 3,5-dimethylpyridine to the oxidant, that Comparative example (l) shows the addition of pyridine to the oxidant, that Example (3) shows the addition of triisopropanolamine, that Comparative example (2) shows the addition of tributylamine to the oxidant and that the Conventional example shows no additives being added to the oxidant. (Table l)
- An anodic electrode foil formed of a dielectric oxide film layer by applying the formation voltage with 90 V to the surface and a cathodic electrode foil are connected with an electrode extracting means and both electrode foils are wound via a separator to form a capacitor element.
- EDT and iron (III) p-toluenesulfonate butanol solution are mixed.
- the capacitor element is impregnated with the mixture. It is then heated at 150 degree for 60 minutes and the polymerization reaction of PEDT occurred in the capacitor element resulting in the formation of a solid electrolyte layer.
- the capacitor element is introduced into an outer package in a closed-end cylindrical form. Further, a sealing member made of elastic rubber is engaged with the open-end section of the package and sealed by using a drawing process, whereby a solid electrolyte layer is constituted. Thereafter, electrical aging is carried out by applying the current whereby a solid electrolytic capacitor is constituted.
- the rated voltage of the solid electrolytic capacitor is 25 WV; its rating capacity is 10 ⁇ F. This solid electrolytic capacitor is compared with the Conventional example. (Example 4" l)
- a solid electrolytic capacitor is constituted in the same manner as that of the Conventional example other than that the capacitor element is impregnated with 2, 6-dimethylpyridine ethanol solution before drying. (Example 4-2)
- a solid electrolytic capacitor is constituted in the same manner as that of the Conventional example other than that 2, 6-dimethylpyridine is added in the EDT and iron (III) p-toluenesulfonate butanol solution mixture, and a 10 wt% solution.
- a voltage (insulation breakdown voltage) is measured by applying the rated voltage 25 V to these solid electrolytic capacitors and increasing the applying voltage with the current value of 50 mV/sec until insulation breakdown occurred. The results are shown in Table 5. (Table 5)
- the voltage resistance property of the Examples compared to the Conventional example has a improvement higher than 10 V and the improved effect on the voltage resistance property of the present invention is indicated.
- the electrical resistance of the solid electrolytic capacitor can be increased exponentially by adhering a Lewis base having a steric hindrance group with a nitrogen atom or a Lewis base having a hydrophilic radical with a nitrogen atom to a surface of the dielectric, or by incorporating them in the electrolyte layer.
Abstract
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Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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JP2009530420A JP5170707B2 (en) | 2006-09-29 | 2007-09-28 | Solid electrolytic capacitor and manufacturing method thereof |
US12/443,274 US20100134956A1 (en) | 2006-09-29 | 2007-09-28 | Solid electrolytic capacitor and method of manufacturing the same |
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PCT/US2006/038025 WO2008039197A1 (en) | 2006-09-29 | 2006-09-29 | Solid electrolytic capacitor and method of manufacturing the same |
USPCT/US2006/038025 | 2006-09-29 | ||
USPCT/US2006/041960 | 2006-10-27 | ||
PCT/US2006/041960 WO2008039214A1 (en) | 2006-09-29 | 2006-10-27 | Solid electrolytic capacitor and method of manufacturing the same |
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WO2008042239A2 true WO2008042239A2 (en) | 2008-04-10 |
WO2008042239A3 WO2008042239A3 (en) | 2008-07-31 |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009147002A2 (en) * | 2008-06-02 | 2009-12-10 | H.C. Starck Gmbh | Process for producing electrolytic capacitors having a low leakage current |
Citations (5)
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US4904701A (en) * | 1986-06-15 | 1990-02-27 | Asahi Kasei Kogyo Kabushiki Kaisha | Process for preparing an ion exchange membrane |
US5082909A (en) * | 1990-10-12 | 1992-01-21 | Hercules Incorporated | Pure tungsten oxyphenolate complexes as DCPD polymerization catalysts |
US5473503A (en) * | 1993-07-27 | 1995-12-05 | Nec Corporation | Solid electrolytic capacitor and method for manufacturing the same |
US5908903A (en) * | 1995-12-27 | 1999-06-01 | Basf Aktiengesellschaft | Metallocene catalyst systems containing lewis bases |
US6421227B2 (en) * | 1999-12-10 | 2002-07-16 | Showa Denko K.K. | Solid electrolytic multilayer capacitor |
-
2007
- 2007-09-28 WO PCT/US2007/020899 patent/WO2008042239A2/en active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4904701A (en) * | 1986-06-15 | 1990-02-27 | Asahi Kasei Kogyo Kabushiki Kaisha | Process for preparing an ion exchange membrane |
US5082909A (en) * | 1990-10-12 | 1992-01-21 | Hercules Incorporated | Pure tungsten oxyphenolate complexes as DCPD polymerization catalysts |
US5473503A (en) * | 1993-07-27 | 1995-12-05 | Nec Corporation | Solid electrolytic capacitor and method for manufacturing the same |
US5908903A (en) * | 1995-12-27 | 1999-06-01 | Basf Aktiengesellschaft | Metallocene catalyst systems containing lewis bases |
US6421227B2 (en) * | 1999-12-10 | 2002-07-16 | Showa Denko K.K. | Solid electrolytic multilayer capacitor |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009147002A2 (en) * | 2008-06-02 | 2009-12-10 | H.C. Starck Gmbh | Process for producing electrolytic capacitors having a low leakage current |
WO2009147002A3 (en) * | 2008-06-02 | 2010-04-01 | H.C. Starck Gmbh | Process for producing electrolytic capacitors having a low leakage current |
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