TWI264745B - Solid electrolytic capacitor - Google Patents

Abstract

To provide a solid electrolytic capacitor having a low ESR characteristic. The capacitor uses a capacitor element of the formed solid electrolyte, an anode foil for use in a capacitor element is set for a porosity of 51% or less after etching, and a cathode foil therefor is set for a porosity of 44% or less after etching. Thus, the conducting part of the electrode foil can be amplified, the resistance part of the electrode foil can be lowered, and a solid electrolytic capacitor having a low ESR characteristic is obtained.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid electrolytic capacitor using a solid electrolyte as an electrolyte. Conventional technology In recent years, the digitization of electronic information devices has progressed, and the speed of driving of the microprocessor (Μ P U ) in the heart of these electronic information devices is progressing. Along with this, the progress of the increase in the power consumption and the reliability caused by the heat release are also prominent, and there is a countermeasure for attempting to lower the driving voltage. Here, a circuit that supplies high-precision power to the microprocessor, a DC-DC converter called a voltage control module (VR Μ ) is widely used, and the output side capacitor prevents voltage drop. Then a series equivalent resistance (ESR) is used by most. As for the capacitor having such a low E S R characteristic, a solid electrolytic capacitor using a solid electrolyte as an electrolyte is being put to practical use, and a capacitor suitable for such use is widely used. However, the drive frequency of the microprocessor is significantly increased, and the power consumption is increased along with this phenomenon. In response to this phenomenon, the increase in the supply power from the capacitor to prevent the voltage drop is required. In other words, it is necessary to supply a large amount of electric power in a short period of time. Therefore, the solid electrolytic capacitor described above is required to have a large capacity, a small size, a low voltage, and a lower E S R characteristic than the conventional one. Here, the solid electrolytic capacitor is described, and after the metal foil of the valve such as giant or bismuth is etched and the surface area is enlarged, the valve is applied to the anode case of the anodized film and the valve metal body of the Ming, Ju or Rui. Applying the worms to the scales of the Chinese National Standard (CNS) Α4 specifications (210Χ297 mm"Τ' " - 4 - (please read the notes on the back and fill out this page) Bureau staff>^t Cooperatives Printing and Printing Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperatives Printing 1264745 A7 B7 _ V. Invention Description (2) Engraving and forming a cathode foil. The anode foil and the cathode foil are interspersed with kraft paper. a spacer such as a polyester (Mylar) synthetic paper, a glass fiber spacer, or a synthetic fiber such as a nylon or a polyester fiber, and an anode is pulled out at any position of the anode foil and the cathode casing. The state of the terminal and the cathode pull-out terminal is taken up, and a capacitor element is formed. A solid electrolyte is formed on the capacitor element, and is housed in a metal case, and is sealed by an epoxy resin or the like. The resin is sealed in the opening of the metal case or inserted into the sealing rubber, and is sealed by a lock-up process. The solid electrolytic capacitor having the above structure is used as an electrolyte, and has a conventional resistivity of 1 Ο Ω Ω - cm ( Compared with the electrolyte of order), a solid electrolyte having a low resistivity of 10 Ω -cm or less is used, and as described above, it is a capacitor having excellent ESR characteristics. However, as for the solid electrolyte, a resistivity has been used for a long time. A few Ω-cm of manganese dioxide, although a solid electrolytic capacitor using a TCNQ complex, a polypyrrole, or a thiophene dielectric having a resistivity of 1 Ω·cm or less is put into practical use, but driven by ΜPU In the progress of re-speeding of the frequency, ESR capacitors which are smaller, larger, and lower are required. According to the inventors of the present invention, in such a solid electrolytic capacitor, the resistivity of the electrolyte is relatively small. Low, but the effect of reducing the ESR of the capacitor is not sufficient. The problem to be solved by the invention is as described above, and only the improvement of the low resistance of the solid electrolyte is desired. The ESR of the low capacitor has its limits. In addition, the ESR reduction is difficult to achieve the paper size. The Chinese National Standard (CNS) Α4 specification (210Χ 297 public Chu) __I____ί______ ______ (please read the back note first) Matters fill out this page again) 1264745 Ministry of Economic Affairs Intellectual Property Bureau Employees' Consumption Cooperatives Printed Β7 Β7 V. Inventions () The problem exists. The present invention is completed to solve the above problems and is provided by using a solid electrolyte having a low resistivity. Solid electrolytic capacitors, and those who achieve low ESR solid electrolytic capacitors. In order to solve the above problems, the inventors have carefully reviewed the results, and by optimizing the porosity of the etching foil used for the electrolytic foil of the capacitor element, it has been found that the electrolytic foil of the capacitor element can be reduced. The inherent resistance 値 makes it possible to further reduce the ESR of the solid electrolytic capacitor. In other words, a solid electrolytic capacitor in which a solid electrolyte is formed on a capacitor element, and an etched foil used for an anode foil of the capacitor element is an uranium engraved foil having a porosity of 51% or less. The etched foil is formed, that is, anodized to obtain the anode of the present invention. Thus, the porosity of the etched foil is set to be less than 51%, which can increase the conductive portion of the anode foil and reduce the resistance portion of the anode foil, and contribute to a low specific resistance solid electrolyte, which can be realized up to the present In the solid electrolytic capacitor having a low ESR characteristic that has not been obtained, if the porosity exceeds 51%, the resistance portion is increased and the desired ESR characteristics are not obtained. Further, when the porosity is 20% or more, it is suitable because a high capacity can be obtained. The porosity of the etched foil herein refers to the enthalpy of the uranium engraved foil void volume divided by the apparent etched foil volume. Furthermore, in the above-mentioned solid electrolytic capacitor, if the foil thickness of the anode foil is 70 μm or more, the resistance of the anode moieties will decrease. ESR will be applicable to the Chinese National Standard (CNS) Α 4 specification (210x). 297 mm)-6 - (Please read the notes on the back and fill out this page)

1264745 A7 B7 V. Description of the invention: If the voltage is set to 7 〇 又 又 又 于 电容器 电容器 电容器 电容器 电容器 电容器 电容器 电容器 电容器 电容器 电容器 电容器 电容器 电容器 电容器 电容器 电容器 电容器 电容器 电容器 电容器 电容器 电容器 电容器 电容器 电容器 电容器 电容器 电容器 电容器 电容器 电容器 电容器 电容器 电容器 电容器 电容器 电容器 电容器 电容器 电容器 电容器m 1 8 Ο μ m The capacitor element is not more than 4% by volume of the capacitor, and when the solid electrolytic component of the cathode semiconductor is increased and not more than 10%, the size can be reduced, so that a solid is formed on the foil thickness. An etched foil of an etched foil used in the cathode of a solid electrolyte device made of an electrolyte. By reducing the resistance of the etched vane to the low-capacitance portion, it is possible to achieve a low-capacitance that has not been achieved until now, but the expected ESR can be obtained if the porosity exceeds 4 4 %. Characteristics, and when it comes up, it is more suitable because of the high capacity available ---- II- m (Please read the notes on the back and fill out this page again.--- Ministry of Economic Affairs Intellectual Property Bureau sv a consumer cooperative In addition, 5 0 to 1 8 are miniaturized, and therefore, 'the capacitors are large, so here, the solid electrolytic capacitors with good heat resistance characteristics that can be obtained by ESR can be realized. If the thickness of the foil of the cathode foil is in the range of ◦ μ 1 , the ESR will be further lowered, and the method can be suitably applied. The electrode of the solid electrolytic capacitor formed by winding the electrode foil described above is long and is essentially caused by the electrode foil itself. The effect of reducing the ESR of the entire resistor capacitor becomes extremely large. When a TCNQ complex is used as the solid electrolyte, the ESR required for the year is a low E SR of 5 to 8 η] Ω. The thiophene dielectric represented by Formula 1 When polymer, beij and CN It is more suitable for the Q complex to have the same characteristics or more, and the capacitor is improved, and it is more suitable. Among them, the reactive, electrical 3,4-extended oxydioxythiophene is preferred. The paper size is applicable to the Chinese national standard (CNS). A4 size (210X 297 mm) -7 - I ! - r I }· II -- Order ____f I, _ 1264745 A7 B7 V. Invention description ()

Ministry of Economic Affairs Zhizhi 3⁄4 Property Bureau employee consumption cooperative printing (in the formula, X means 〇 or S, X is 〇, A is alkyl or polyoxyalkylene, X is at least ~ test is S, 厶An alkyl group, a polyoxyalkylene group, a substituted alkylene group, or a substituted polyoxyalkylene group, wherein the substituent is an alkyl group, an alkenyl group or an alkoxy group. Further, as for a solid electrolyte, when manganese dioxide is used, The embodiment of the present invention is specifically described in the embodiment of the present invention. The aluminum foil is roughened by an alternating current etching method in a saturated liquid obtained from an aqueous solution of hydrochloric acid or the like to form a porosity. 5 1 % or less. In addition, a dielectric film is formed and formed in a liquid to be formed by a phosphoric acid aqueous solution or the like to prepare an anode foil, whereby the porosity of the etching foil is set to 5 1 % or less. Preferably, it is 43% or less, more preferably 7% or less, and the conductive portion of the anode foil is increased and the resistance portion is lowered to lower the ESR of the solid electrolytic capacitor. Thus, in the present invention, by reducing the porosity, Increase the conductive portion of the electrode foil and try to reduce E SR, so the state of the depth scale or area ratio of the etched pits (please read the back of the page and fill in the page) -3 ·1 l*li — — 1 ml 03⁄4 . , v5 έ This paper size applies. China National Standard (CNs) A4 Specification (210X'297 mm)-8 - 1264745 A7 ____ B7 6 --- V. Invention Description () (Please read the note on the back and fill out this page) 'For example, even after etching The effect of the present invention is not reduced in the state where the depths of the etched pits on both sides of the foil are different. Further, in order to ensure the maximum volumetric volumetric efficiency, if the porosity is 2% or more, the etching area is increased. If the foil thickness of the anode foil is above 7 Ο μ m, preferably above 9 〇μm, the resistance of the anode foil is reduced and E sr is reduced, if 18 μ μ When m is less than or equal to 150 μm or less, the volumetric efficiency of the capacitor is increased, and the size can be reduced, so that the film thickness is 70 to 180 μm, and more preferably 90 to 150 μππ}. The aluminum foil is roughened by AC etching or chemical etching as in the anode foil 'by setting the porosity to 4 4% or less, preferably 35% or less, more preferably 26% or less, to prepare a cathode foil. In this way, the resistance of the cathode foil is lowered, and the ESR of the solid electrolytic capacitor is lowered. Further, the maximum capacity is ensured. The volumetric efficiency, if the porosity is 1% or more, the etching area is increased, and a high capacity is obtained, so that it is suitable. Further, the thickness of the cathode is 5 〇 to 180 μη], preferably 70 〜 When 15 〇 μιπ, more preferably in the range of 70 to 1 0 0 μm, the ESR can be further lowered, and it is preferable to be miniaturized. Printed by the Intellectual Property Office of the Ministry of Economic Affairs, the consumer cooperatives, using a low-resistance organic semiconductor to reduce the porosity and increase the conductive portion of the electrode foil, by drawing back the electrode foil. The resistance 每 of each unit area, that is, the resistance 値 (hereinafter referred to as foil resistivity) between the end faces of the square square electrode foil, the box width and the foil area are optimized, and the E s R of the capacitor can be further reduced. That is, the resistivity is 1 〇Ω · cm or less. The organic semi-conducting paper scale is applicable to the Chinese National Standard (CNS) A4 specification (2丨0Χ 297 mm) 1264745 Α7 Β7 5. Inventive Note () The low resistivity characteristic of the organic semiconductor can be maximized by using the following electrode foil '. The electrode foil foil used in the present invention has a resistivity of 〇.1 5 〇.6 m Ω , more preferably 〇 · 1 7 〇 · 4 5 m Ω. By using the electrode foil of this range, the resistance portion of the electrode foil is lowered, and E S R is lowered. If the range is less than this, the effect of reducing E S R is small, and if it exceeds this range, the rate of decrease of E S R is lowered. Therefore, the foil width is 3 to 16 m m, preferably 5 to 14 m m. When this range is not reached, even if the foil resistivity is lowered, it contributes greatly to the resistance portion of the electrolyte, so that E S R does not decrease. When it exceeds this range, the rate of decrease of ESR is reduced, and the length of the capacitor element is increased, the impregnation property of the organic semiconductor is lowered, the retention of the electrolyte is lowered, and the ESR is increased. Therefore, the foil area needs to be 300 mm 2 or more. It should be more than 500 mm 2 or more. When this range is not satisfied, the area of the electrode foil and the electrolyte is small, and the resistance 値 is not lowered, so E S R does not decrease. Therefore, since the capacitor element of the solid electrolytic capacitor of the present invention is formed by interposing a spacer through a spacer, the foil of the electrode foil can be made longer. As a result, a sufficient foil area is obtained and E S R is lowered. Here, as described above, the cathode foil is an etched foil, and the anode foil is applied to a liquid to be formed by a phosphoric acid aqueous solution or the like to cause the etching foil to be energized, and an oxide film is formed on the surface. Therefore, the electrode foil is composed of a portion of aluminum that is not pre-etched (hereinafter referred to as a residual core) and an etched portion, and an anode foil is formed by a portion of the oxidized film, but by setting the degree of the residual core to 50. ~ 17 0 μ m, more preferably set to 60 0~1 5 0 μ m, can foil the electricity (please read the back of the note before you fill in this page) Pack ·--- Order --- Ministry of Economics intellectual property Bureau employees' consumption cooperatives printed this paper scale applicable to China National Standard (CNS) A4 specifications (210Χ297 mm) -10 - 1264745 Ministry of Economic Affairs Intellectual Property Bureau employees Bone Cooperatives Printing A7 B7 V. Invention Description (8) Resistance coefficient Set to 0 · 1 5~0 · 6 m Ω, more preferably 0 · 1 7~ 0 · 4 5 m Ω. Further, when the thickness of the residual core is too large, the winding back operation becomes difficult, so the thickness of the residual core should be 1 〇 〇 μ m or less. Here, as for the organic semiconductor, if a T C N Q complex is used, a low ESR of E 6 of 4 to 6 ή Ω which has been required in recent years can be realized. Further, as for the organic semiconductor, even if a conductive polymer is used, ESR can obtain properties equivalent to or higher than those of the TCNQ complex, and when a polymer of a thiophene dielectric represented by a conductive polymer (Formula 1) is used, It is preferable that the heat resistance of the capacitor is improved, and among them, 3,4 ethoxythiophene which is excellent in reactivity and electrical properties is preferable. In addition, the thickness of the foil or the foil length of the electrode foil of the above-mentioned electrode foil is not as small as possible, but the conductivity of the conductive polymer having a low electrical resistivity is lowered to reduce the porosity. The roll-back type surface-mounted solid electrolytic capacitor in which the conductive portion of the electrode foil is enlarged can reduce the ESR of the capacitor by optimizing the foil resistivity and the foil width and the foil area. In other words, by using a conductive polymer having a resistivity of 0.1 Ω·cm or less, the following electrode foil can be used to maximize the low resistivity of the conductive polymer, and it is possible to achieve a long-term Some solid electrolytic capacitors with low ESR characteristics. The electrode foil foil used in the present invention has a resistivity of 0 · 27~0 · 7ηιΩ, more preferably 〇 · 34~ 〇 . 5 5 m Ω. By using the electrode foil of this range, the resistance portion of the electrode foil can be lowered and the E S R can be lowered. When the range is less than this range, the ESR reduction effect is small. If it exceeds this range, the ESR reduction rate will be reduced. The paper standard is applicable to the Chinese National Standard (CNS) A4 specification (2丨〇: <297 mm) —Chuan Yi (please read the notes on the back and fill out this page)

1264745 A7 B7 V. INSTRUCTIONS () 〇 Therefore, as described above, the foil resistance coefficient I of the electrode foil is affected by the stomach 0 · 27~〇·7] ήΩ, more preferably 〇.34~〇.55]όΩ (please Read the precautions on the back and fill out this page. 'The residual core thickness can be 4〇~1〇0 pm, more preferably 5〇~8〇μ1Ή. Therefore, when a thiophene-derived polymer represented by the formula 采用 is used as the conductive polymer, since the low resistivity characteristic of 〇·1 Ω·cm or less is used, the ESR of the capacitor can be lowered, and the heat resistance of the capacitor can be made. It is more suitable for the characteristic pick-up, and it is preferable to use 3,4 ethoxy thiophene with good reactivity and good electrical properties. Further, when a film of 0·1 to 10 V is formed on the cathode case, and it is preferable to form a film of q. 3 to 5 V, E S R is lowered, and high-temperature life characteristics can be improved, which is preferable. Further, when a metal compound having a low oxidizing property such as titanium nitride or titanium or a layer made of a metal is formed on the surface of the cathode foil, the electrostatic capacity is increased, which is preferable. Here, it is preferable to form a film on the cathode foil to form a film on which a metal having a low oxidizing property or a metal compound is formed on the film. Printed by the Intellectual Property Office of the Intellectual Property Office of the Ministry of Economic Affairs. The anode pull-out terminal is mounted on the above anode foil and cathode foil, and the cathode is pulled out of the terminal, and the spacer is rolled back through the spacer. Thereafter, a dielectric oxide film which can be repaired in the step of applying a voltage to the present solution is used, and the anode foil of the present invention and the conventional cathode foil, the conventional anode foil and the present invention are used. The cathode foil of the invention can obtain the effect of the invention, but by using both the anode foil and the cathode foil of the invention, the largest paper scale can be applied to the Chinese National Standard (CNS) A4 specification (210X_297 mm) - 12 - 1264745 A7 B7

Γ ' TD V. Invention Description () Effect. (Please read the precautions on the back and fill out this page.) Here, as for the spacer, non-synthetic fibers such as Manila paper, kraft paper, glass spacers, or vinyl alcohol (Vinyl) or polyester can be used. For the fabric, a porous spacer may be used. Further, when the pull-out terminal is attached to the electrode foil, when the electrode foil having the conductive portion of the present invention is used, the contact resistance of the joint portion between the electrode foil and the pull-out terminal is lowered, and the ESR of the solid electrolytic capacitor is further Lowering Next, the case where a TCNQ complex is used as a solid electrolyte will be described. The T C N Q complex is melted and liquefied in a cylindrical metal casing made of aluminum and placed on a heated planar heater. Therefore, the pre-heated capacitor element is immersed, the metal casing is immersed in the cooling water, and the T C N Q complex is cooled and solidified. Further, an epoxy resin is injected into the casing to heat-harden it in the high temperature gas cell. Thereafter, a heating voltage was applied and aged to prepare a solid electrolytic capacitor. The Ministry of Economic Affairs, the Intellectual Property Co., Ltd. employee-sponsored co-operatives, and the use of poly(3,4 ethoxylated thiophene) (PEDT) as a solid electrolyte in the polymer of 3,4-ethoxy thiophene (EDT) The capacitor element is immersed in a mixed liquid prepared by mixing EDT and an oxidizing agent with a predetermined solvent, and a polymerization reaction of ED is performed in the capacitor element to form a solid electrolyte layer made of PEDT. Therefore, the capacitor element is inserted into the metal casing, and the sealing rubber is inserted into the open end portion to be sealed by the locking process to complete the solid electrolytic capacitor. As for the aforementioned EDT, EDT monomers can be used, but it is also possible to use a single paper wave scale of EDT and volatile solvent in a volume ratio of 1:0 to 1:3. Applicable to the Chinese National Standard (CNS) A4 specification (210x 297)公)) -13 - Ministry of Economic Affairs, Intellectual Property Bureau, Consumer Cooperatives, Printing 1264745 A7 __ B7 11 V. Inventions ()

Bs ί谷液. As the volatile solvent, a hydrocarbon such as pentane, an ether such as tetrachlorofuran or an ester such as ethyl formate, an ketone such as acetone, an alcohol such as methanol, or a nitrogen compound such as B may be used. Among them, it is preferably methanol, ethanol, acetone or the like. Further, depending on the oxidizing agent, an aqueous solution of iron p-toluenesulfonic acid, periodic acid or iodic acid which has been dissolved in butanol may be used, and the temperature of the oxidizing agent to the solvent is preferably 4 〇 to 55 5% by weight. If it is less than this range, ε SR will rise. If it exceeds this range, the electrostatic capacity will decrease. The mixing ratio of D Τ and oxidizing agent (excluding solvent) is preferably in the range of 1 · 0 · 9 to 1 : 2 · 2 by weight. Outside this range, 'E S R will rise. The reason can be considered as follows. That is, if the amount of the monomer oxidizing agent is too large, the amount of the relatively impregnated monomer is lowered. Thus, the amount of P E D 形成 formed is lowered, and E s r is increased. On the other hand, if the amount of the oxidizing agent is too small, the amount of P E D 形成 formed by the oxidizing agent required to polymerize the monomer is reduced and the E S R is increased. E D 在 and other polymeric monomers which have been described herein may be employed. As the polymerizable monomer, aniline, pyrrole, furan, acetylene or the like can be oxidatively polymerized by a predetermined oxidizing agent, and can be used if a conductive polymer can be formed. Further, as for the inorganic electrolyte in the solid electrolyte, manganese dioxide may be used, and after the capacitor element has been immersed in the aqueous solution of manganese nitrate, heat treatment is performed at 3 〇 4 to 400 ° C. Thereafter, a voltage applied to the resultant liquid is again applied to repair the damaged dielectric film in the heat treatment. This manganese nitrate aqueous solution is repeatedly immersed, heat-treated, and repaired to be formed several times. Finally, heat treatment is carried out at 4 0 0~0 0 °C, and repaired again. This paper scale applies to China National Standard (CNS) A4 specification (210x 297 mm) _ 14 - -------- ·-----:----Book-------I------1 (Please read the notes on the back and fill in this page) 1264745

generate. Thus, a capacitor element in which manganese dioxide used as a solid electrolyte has been formed is placed in an outer casing, an epoxy resin is injected, and heat is hardened and sealed to form a solid electrolytic capacitor. Lead dioxide can also be used as such an inorganic electrolyte. EXAMPLES Hereinafter, a solid electrolytic capacitor of the present invention will be specifically described by way of examples. (Example 1) An example in which a T C N Q complex was used as a solid electrolyte was described. The aluminum foil is roughened by alternating current etching, and is formed by forming a dielectric oxide film, and the anode foil of the present invention is produced, and the same as the aluminum foil is roughened by alternating current etching on the surface. A chemical film is formed and a cathode foil is produced. Between the anode foil and the cathode foil, an anode pull-out terminal is attached to each of the spacers made of Manila paper, and the cathode is pulled out of the terminal and pre-wound. Thereafter, a voltage is applied to the generated liquid, and the wound dielectric film can be repaired to form a damaged dielectric oxide film. On the other hand, a TCNQ complex was placed in a cylindrical metal casing formed by Ming, and placed on a planar heater heated to about 280 °C to melt the TCNQ complex. . The foregoing capacitor element preheated to about 300 ° C was dipped therein, and the metal casing was immediately immersed in cooling water and the T C N Q complex was cooled and solidified. Furthermore, a required amount of epoxy resin is injected into the outer casing to heat-harden in a high-temperature gas enclosure, and then a rated voltage is applied between the terminals for 1 hour in 1 2 5 t: and aged, and the paper scale is applied. China National Standard (CNS) Α4 Grid (210X 297 mm) -15 - (Please read the notes on the back and fill out this page I n —-I- 1 ιί·1 Booked by the Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative 6% of the foil 3 9 % of the 1264745 A7 B7 ~- Τ 3 " ------ 5, invention description () and get a 04xl 0 L solid electrolytic capacitor. (Case 1 - 1) In the solid electrolytic capacitor thus formed, a box having a thickness of 1 Ο Ο μ m and a porosity of 26% after being hungry is used as an anode, the thickness is 8 5 μm, and the porosity after etching is 19%. The foil was used as the cathode foil' as Example 1 - 1. (Example 1 - 2) The thickness was 1 Ο Ο μ m, and the porosity after etching was 4 as the anode foil, and the thickness was 5 Ο μ m, after etching. The porosity is a foil as a cathode foil, as Example 1-2. (Examples 1 to 3) Except for the thickness of 1 Ο Ο μ m, after etching A solid electrolytic capacitor was produced by the same means as in Example 1 to 2, and the thickness was 1 Ο Ο μ m. (Examples 1 to 4) Further, the thickness was 1 Ο Ο μ m. After the etching, the porosity was 52% as the anode foil, and a foil having a thickness of 75 μm and a porosity of 52% after etching was used as the cathode foil as Example i-4. ) The paper size applies to the Chinese National Standard (CMS) A4 specification (210X297 public | - ....... _i n lit - - 1 jj · in . (Please read the notes on the back and fill out this page) Ministry of Economic Affairs, Zhici Property Bureau, Selling Consumers Cooperative, Printed 1264745 A7

IT invention description A case of a thickness of 1 〇Ο μ m 5 is used as the anode foil, and a foil having a thickness of 5% is used as the cathode foil. The porosity after etching is 52 % 〇μ m, and the porosity after etching is the foil resistance of the anode foil of Table 1 and the solid electrolytic capacitors of the examples 1 to 1 to 4 and the conventional example. A comparison table of ESR. table

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-I- m 'IT 4 Ministry of Economic Affairs Intellectual Property Bureau P' Industrial Consumer Cooperative Printing Table 1 shows an example of using the anode foil of the present invention 丄-2, 1-3' using the cathode foil of the present inventionχ A4 is lower in ESR than the conventional example. Further, the embodiment 1 - 1 which uses an anode foil having a porosity of 26% and a cathode foil of 91% is reduced to 5 · 8 m Ω ' to achieve a low E S R which has never been seen before. Further, Example 1 - 3 series E S R having an anode foil having a porosity of 33% was used, and Example 1 to 2 having an anode foil having a porosity of 4 6 % was used.豕 Paper scale applicable to China National Standard (CNS) A4 specification (210X 297 mm) -17 1264745 A7 B7 V. Inventive Note () It is also known that the hole is reduced from the conventional example to the embodiment 2 6~4 6 %, the foil resistance is reduced from 2 3 1 m Ω / ηι to 7 5~1 5 3 ηι Ω / m, the conductive portion of the electrode foil is increased, and the resistance portion is lowered. Further, in the comparative example, a capacitor element was formed in the same manner as in Example 1-1. An electrolytic solution having a low resistivity characteristic was impregnated into the capacitor element to form an electrolytic capacitor. The electrolyte used was > - butyrolactone 7 5 points, and the oxadicarboxylate key was 25 minutes. The obtained E S R system showed a enthalpy of up to 5 2 m Ω. Even when the electrode foil of the present invention was used, if the solid electrolyte having low resistivity characteristics was not used as the electrolyte, it was found that the effects of the present invention were not obtained. (Example 2) Next, an example in which P E D T was used as a solid electrolyte will be described. As for the spacer, a non-woven fabric made of a nylon fiber is used, and a layer made of titanium nitride is formed on the film to be formed on the cathode foil, and the capacitor element is formed in the same manner as in the first embodiment. Generated. Therefore, the formation of a solid electrolyte was carried out as follows. A mixture of E D T and 45 % p-toluenesulfonic acid iron in butanol was poured into a cup-shaped container to make a weight ratio of 1:0 · 8 to prepare a mixed solution. Therefore, the capacitor element was immersed in the above mixture for 1 minute. Therefore, heating at 1 20 ° C for 1 hour was carried out to cause polymerization of P ED in the capacitor to form a solid electrolytic layer. Therefore, this capacitor element was inserted into a bottomed cylindrical aluminum casing, and the opening was rubber-sealed by pultrusion to carry out an aging test to prepare a solid electrolytic capacitor of 1 〇 0 x 10 L. Therefore, the production of the Chinese National Standard (CNS) A4 specification (210X 297 羡) has been adopted and this paper scale has been adopted. _ 18 - (Please read the back of the note first; refill the item, write this page) Ministry of Economics Intellectual Property Bureau employee consumption cooperative printed 1264745 A7 B7 — - V. Inventive Note () The solid electrode electrolytic capacitor of the same electrode foil of Example 1 was formed into Examples 3 - 1 to 3 - 4 and Conventional Example 3. The E S R comparison of these solid electrolytic capacitors is shown in Table 2. [Table 2] Anode foil cathode foil ESR porosity, foil thickness, porosity, foil thickness (m Ω ) (%) (μ m ) (%) (μ m ) Example 2-1 26 1 00 19 85 5.0 Example 2-2 46 1 00 39 50 6.8 Example 2-3 η 〇 100 3 9 50 7.2 Example 2-4 52 100 22 75 6.8 Conventional Example 2 52 1 00 3 9 50 8.1 As can be seen from Table 2, in the examples 2 shows the same results as in Example 1, and the effects of the present invention are apparent. (Example 3) Next, a solid electrolytic capacitor of a wafer type having a surface of a capacitor of 6.30 x 6 L was fabricated, and a solid electrolytic capacitor fabricated in the same manner as in Example 1 was used as Example 3 - 1 , 3 - 2 , Conventional Example 3 - 1 , the solid electrolytic capacitor produced in the same manner as in Example 2 is the embodiment 3 - 3 to 3 - 6, the conventional example 3 - 2, the porosity of the electrode foil used and the paper size Applicable to China National Standard (CNS) A4 Specification (210X297 mm) -19 - (Please read the notes on the back and fill out this page to order the Ministry of Economic Affairs, Smart Finance 1 Bureau (Working Consumer Cooperative Printed 1264745)

A

7 B V. Description of invention (7) Foil thickness, and ESR of these solid electrolytic capacitors are shown in Table - 3 [Table 3] Anode foil cathode foil solid electric ESR porosity ratio foil thickness porosity solution thick solution Mass (m Ω ) (%) (μ m ) (%) (μ m ) Example 3 Ί 26 100 1 9 85 TCNQ 17.9 Example 3-2 η 〇 JJ 100 39 50 TCNQ 22.2 Example 〇 〇 JJ 26 1 0 0 19 85 PEDT 14.3 Example 3-4 46 100 39 5 0 PEDT 17.4 Example 3-5 η η JJ 100 3 9 50 PEDT 18.3 Example 3-6 52 100 22 75 PEDT 1 7.4 Conventional Example 3-1 52 1 00 39 50 TCNQ 23.7 Conventional Example 3-2 52 100 39 50 PEDT 19.7 (Please read the notes on the back and then fill out the page. Ministry of Economic Affairs, Intellectual Property Office, Staff Consumer Cooperatives, printed in Table 3, in Example 3 The wafer type solid electrolytic capacitor also showed the same results as those of Examples 1 and 2. Further, the anode foil having a porosity of 26% and the cathode foil having a porosity of 19% were used in Example 3-1. 3 - 3 Compared with the conventional examples 3 - 1 , 3 - 2, the ESR system is reduced by 5 · 8 m Ω and 5 · 4 m Ω, respectively, and the effect of the present invention is also increased. Example 3 - 3 using PEDT as electrolyte, and 3 · 6 m Ω lower than Example 3-1 using TCNQ complex, achieving the Chinese paper standard (CNS) A4 specification (210X297 public) PCT) -20 - 1264745

^ 18, invention description () Es R characteristics that have never been seen in wafer type solid electrolytic capacitors. Further, when a solid electrolytic capacitor of Example 3 - 3 to 3 - 6 using PEDT as a solid electrolyte was subjected to a peak temperature and a lead-free flattening heat treatment (reflow) test at 250 ° C, no static capacity was observed, and ESR was The change can be seen in correspondence with the lead-free heavy flow system. (Example 4) Next, an example in which manganese dioxide is used as a solid electrolyte will be described. After the capacitor was immersed in a 40% aqueous manganese nitrate solution, heat treatment was performed at 350 °C. Thereafter, a voltage is applied to the formation liquid again, and the dielectric film damaged by the heat treatment is repaired and generated. This manganese nitrate aqueous solution is immersed several times, heat treated, and repaired to form. Finally, heat treatment was carried out at 405 Torr and repaired again. The capacitor element in which the solid electrolytic manganese dioxide was formed was housed in an outer casing, and an epoxy resin was injected to heat-harden and hermetically seal to form a 1000 x 10 L solid electrolytic capacitor. Therefore, the same electrode foil as in Example 1 was used as the aperture ratio and foil thickness of the electrode foil used in Examples 4-1, 4-2 and 4, and the ESR of the solid electrolytic capacitors was shown. In ^ Table 4. I (please read the note on the back and then fill out this page) Ordering Ministry of Economic Affairs Intellectual Property Bureau i Industry Consumer Cooperative Printed Paper Size Standard Applicable to China National Standard (CNS) A4 Specification (210Χ'297 mm) -21 > 191264745 A7 B7 Five invention description Table 4 〕 Anode foil stalk bean foil esr porosity rate foil thickness porosity (m Q ) (%) (μ m ) (%) (μ m ) Example 4-1 26 1 00 1 9 85 14.6 Example 4 - 2 33 1 00 39 50 17.7 Conventional Example 4 52 1 00 39 50 20.1 As is apparent from Table 4, the same results as in Example 1 are shown in Example 4, and the effect of the present invention It is obvious and obvious. Further, the present invention is not limited to the above-described embodiment, and the manufacturing conditions of the solid electrolytic capacitor for forming conditions and the like for the mites can be appropriately selected. Further, it is not particularly limited to a coil type solid electrolytic capacitor, and may be applied to a laminate shape or the like. Next, an organic semiconductor is used to explain an embodiment of a coil-type solid electrolytic capacitor in which a foil resistivity, a foil width, and a foil area have been specified. (Example 1) An example in which a T C N Q complex was used as an organic semiconductor was described. The aluminum foil was roughened by alternating current etching, and both were formed to form a dielectric oxide film, and the anode foil of the present invention was produced. Further, similarly to the aluminum foil, the surface was roughened by alternating current etching, and a chemical film was formed on the surface to prepare a cathode foil. Between the anode foil and the cathode foil, the Chinese National Standard (CNS) A4 specification (2丨0 X 297 mm) is applied to the paper scale by Manila paper -22 - ml 11-! I - · 11 =- Ml «—-1— * (Please read the notes on the back and fill out this page) Order the Ministry of Economic Affairs Intellectual Property Bureau P' Gongxiao t Cooperative Print ^ 1264745 A7 B7

-- JQ V. Inventive Note () The spacer is installed with anode pull-out terminals at any position, the cathode is pulled out of the terminal and pre-rolled, and then a voltage is applied to the generated liquid, which can be repaired by coiling. A damaged dielectric oxide film is formed. (Please read the precautions on the back and fill out this page.) On the other hand, put the TCNQ complex in a cylindrical metal casing made of aluminum and place it on it to about 280 °C. On the flat heater, the TCNQ complex was melted and liquefied. The foregoing capacitor element preheated to about 300 ° C was dipped therein, and the metal casing was immediately immersed in cooling water and the T C N Q complex was cooled and solidified. Furthermore, a required amount of epoxy resin is injected into the outer casing to heat-harden in a high-temperature gas enclosure, and then a rated voltage is applied between the terminals at 1 2 5 ° C for 1 hour and aged to form a solid electrolytic capacitor. . Therefore, the anode resistive foil foil, the foil area, the residual core thickness and the respective foil foils of the anode foil and the cathode foil used in Examples 1 - 1 to 1 - 3 and Comparative Example 1 - 1 to 1 - 4 of the solid electrolytic capacitor thus formed The ESR of the solid electrolytic capacitor is shown in Table 5. Further, the foil thicknesses of Examples 1 to 1 to 1 to 3 are each 1 1 〇 μ m, 1 1 5 μ m, and 1 4 Ο μ m. Ministry of Economic Affairs, Intellectual Property Bureau, S-consumer, Cooperatives, Printed with Appropriate Ruler Paper - This SNC is a « 榡 « 647 1264745 A7 _______ B7, Invention Description (21) [Table 5] Foil Resistance Foil Foil Area Residual Core Thick ESR (m Ω ) (mm) (mm2) (μηι) (m Ω ). Example 1 0.40 6 1000 65 5 . 8 Example 1-2 0.4 1 1 1 1850 64 3.9 Example 1-3 0.25 6 800 1 02 5.7 Comparative Example 1-1 0.89 6 1950 32 8 . 1 Comparative Example 1-2 0.22 2 2100 119 9.8 Comparative Example 1-3 0.40 20 3 400 65 7.1 Comparative Example 1-4 0.17 1 5 250 145 11.2 I _ (Please read the precautions on the back side and then fill out this page) - Packing --- It can be clearly seen from Table 5 that the solid electrolytic capacitor of Embodiment 1 -1 to 1 - 3 of the present invention shows E s The effect of the present invention is as low as R below 6 1 Ή Ω. In contrast, the comparative example 1 to 1 in which the foil resistivity is 0·6 m Ω or more has a height of 8 · Ι π Ω even though the foil area is 195 〇 mm 2 larger than that of the embodiment 1-1 to 1-3. . In the comparative example 1 to 2, which has a width of 3 ni m or less, the resistivity of the foil is 〇· 2 2 The Intellectual Property Office of the Ministry of Economic Affairs, the employee Xiaohuang Cooperative, printed ιώ Ω, which is also lower than the embodiment 1 - 1 to 1 - 3 Furthermore, although the foil area is 2,100 m 2 which is larger than that of the embodiment 1 to 1 to 1 - 3 , it is as high as 9 · 8 m Ω. The ESR of Comparative Example 1 to 3 having a foil width of more than 16 m is also as large as 7. 1 η] Ω. Further, the comparative example 1 - 4 series foil having a foil area of 3 mm 2 or less has a resistivity of 0.17 m Ω, although smaller than the embodiment 1 -1 to 1 - 3, the ESR is as large as 1 1 · 2 This paper scale is suitable for the wealth of KNS. Α 格 (' 21QX297 mm) -24 - 221264745 A7 B7 Ministry of Economic Affairs Zhici Property Bureau, the consumption of consumer cooperatives printed five, invention description () m Ω 〇 and In the capacitor element formed by the same method, an electrolytic capacitor in which an electrolytic solution having a low resistivity characteristic was impregnated was prepared as Comparative Example 1 - 5 , and an electrolytic capacitor in which manganese dioxide had been formed was produced. As Comparative Example 1 - 6 . The electrolyte solution of Comparative Example 1 to 5 was used for 7 5 minutes, and benzodimethyl ester ethyl dimethyl imidazolinium 2 5 minutes. The obtained ESR systems each represent a enthalpy of up to 5 2 m Ω and 17 m Ω. Even if the electrode foil of the present invention is used, if an organic semiconductor having a low resistivity characteristic is not used as the electrolytic ruthenium, the present invention is not obtained. Known after the effect. (Embodiment 2) Next, an embodiment in which P E D is used as an organic semiconductor will be described. As the spacer, a non-woven fabric made of a nylon fiber is used, and a layer made of titanium nitride is formed on the film to be formed on the cathode foil. Otherwise, a capacitor element is formed in the same manner as in the first embodiment, and repaired. generate. Therefore, the formation of an organic semiconductor was carried out by injecting a solution of E D T and 45% of a p-toluenesulfonic acid iron in butanol to a weight ratio or a ratio of 1 : 〇 8 ' in a cup-shaped container. Therefore, the capacitor was immersed in the above mixture for 10 seconds. Therefore, heating was carried out at 1 2 ° C for 1 hour to cause polymerization of P E D T in the capacitor element to form an organic semiconductor layer. Therefore, the capacitor element was inserted into a bottomed cylindrical aluminum casing, and the opening was rubber-sealed by deep drawing to cause aging to produce a solid electrolytic capacitor. The foil of the electrode foil of the examples and comparative examples used here (please read the note on the back of the page and then fill in the page) This paper size applies to the Chinese National Standard (CNS) A4 specification (210X 297 mm) -25 - 1264745 A7 V. INSTRUCTIONS (23) The coefficient of resistance, the width of the foil, the thickness of the residual core, and the ESR of the respective solid electrolytic capacitors are shown in Table 6. And the thickness of the foil of Example 2~2-3 is 1 1 5 μ η!, 1 1 〇μ m , 1 3 5 μ ηι ° [Table 6] Foil Resistance Foil Foil Area Residual Core Thickness ESR (m Q ) (mm) (mm2) (μΐΏ) (m Ω ) Example 2-1 0.4 1 6 1050 6 3 5.] Example 2 - 2 0.40 11 1800 65 3 . 5 Example 2 - 3 0.24 6 850 105 4.9 Comparative Example 2 - 1 0.80 6 1450 30 7.2 Comparative Example 2 - 2 0.2 1 2 2 15 0 12 1 8.6 Comparative Example 2 - 3 0.40 20 3 3 5 0 64 6.5 Comparative Example 2-4 0.17 15 240 1 50 9.0 II Ϊ . · · I—S1 I] —m· ml : I— ft— 1· (Please read the notes on the back and fill out this page) Ordering the Ministry of Economic Affairs Intellectual Property Bureau Employees Consumption Cooperatives Printed in Table 6 The same results as in Example 1 were also shown in Example 2, and the effects of the present invention are apparent. Next, an electroconductive polymer is used, and an embodiment in which a solid electrolytic capacitor for actually mounting a surface of a winding type having a foil width and a foil area is specified is described. An example in which P E D is used as the conductive polymer will be described, and secondly, P E D T is an example of an organic semiconductor. As for the spacer, a non-woven fabric made of nylon fiber is used, and a film is formed on the cathode foil. The paper is applicable to the Chinese National Standard (CN'S) A4 specification (210X297 mm) _ 26 - 1264745 A7 B7 — V. Invention On the explanation (), a layer made of titanium nitride was formed, and otherwise, a capacitor element was formed in the same manner as in Example 1, and repaired and produced. Therefore, the formation of an organic semiconductor was carried out by injecting E D T and 45 % of a solution of iron p-toluenesulfonate in a cup-shaped container to a weight ratio of 1:0. 8. Prepare the mixture. Therefore, the capacitor was immersed in the above mixture for 1 sec. Therefore, heating at 1 2 ° C for 1 hour causes polymerization of P E D T to occur in the capacitor element to form a solid electrolyte layer. Therefore, the capacitor element was inserted into a bottomed cylindrical aluminum casing, and the opening was rubber-sealed by deep drawing to cause aging to produce a solid electrolytic capacitor. Therefore, the solid resistive capacitors of Examples 1 to 3 thus formed, the foil resistivity of the anode foil and the cathode foil used in Comparative Examples 1 to 4, the foil width, the foil area, the thickness of the residual core, and the ESR of the respective solid electrolytic capacitors are shown in Table 7. Further, the thicknesses of Examples 1 to 3 were each of 9 5 μm, 9 μm, and 120 μm. I------^·--- (Please read the notes on the back and fill out this page). The Ministry of Economic Affairs, Intellectual Property Office, Staff and Cooperatives, Co., Ltd. Printed I Paper Scale, China National Standard Rate (CNS) A4 Specification (210: < 297 mm) -27^ 1264745 A7 B7 25 V. Inventive Note () [Table 7] Foil Resistance Foil Foil Area Residual Core Thickness ESR (m Ω ) (mm) (mm2) (μηι One (m Ω ) Example 1 0.55 2.2 240 50 13 Example 2 0.56 3 320 50 10 Example 3 0.34 2.2 1 70 80 __ 1 4 Comparative Example 1 0.9 1 2.2 335 3 1 17 Comparative Example 2 0.3 1 1 360 85 20 Comparative Example 3 0.32 2.2 110 84 1 9 (Please read the notes on the back and fill out this page) Printed by the Ministry of Economic Affairs, Zhici Property Bureau, Staff Consumer Cooperatives, as shown in Table 7, Examples 1 to 3 of the present invention The solid electrolytic capacitor is a crucible having an ESR as low as 15 m Ω or less, and the effects of the present invention are known. On the other hand, Comparative Example 1 in which the foil resistivity was 〇. 7 m Ω or more, although the foil area was 3 3 5 m 2 2 was larger than that of Example 1 to 3, and became as high as 17 m Ω. In Comparative Example 2, in which the foil width was 1 · 5 mm or less, the foil resistivity was 0 · 3 1 m Ω, which was also lower than that of Examples 1 to 3. Further, although the foil area was 366 mm 2 compared with Example 1 - 3 large, also become as high as 20 m Ω. In Comparative Example 3, which had a foil area of less than 150 m 2 , the foil resistivity was 0 · 3 2 m Ω, although it was smaller than the example 丨 〜 3 and the E S R was as large as 19 m Ω. Further, as for Comparative Examples 4 and 5, a capacitor element was formed in the same manner as in Example 1, in which a butyl CNQ complex was formed in each of the capacitors, and ~e~ oxidized as a solid electrolyte, and the obtained ESR lines each represented as high as q π. ^ 二* 丄7 m Ω This paper scale applies to China National Standard (CNS) Α4 specification (2Ι0Χ 297 mm) 1264745 A7 B7 —5, invention description (), 6 1 m Ω, even with the electrode of the invention If the foil does not use a conductive polymer having a low resistivity characteristic as an electrolyte, the effect of the present invention is not known. As described above, according to the present invention, in the case of the solid electrolytic capacitor using the solid electrolyte as the electrolyte, the porosity after etching of the anode foil used for the capacitor element is set to 51% or less, and the cathode The porosity after the etching of the foil is set to 4 4% or less, and a solid electrolytic capacitor having a low ESR characteristic which is not currently available can be realized. 1 - I f « 1ι·-1- ί!0 ! ·ι_ί 11 - (Please read the notes on the back and fill out this page.

XI Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing This paper scale applies Chinese National Standard (CNS) A4 specification (210 X 297 mm) -29 -

Claims (1)

1264745 ABCD Ministry of Economic Affairs Intellectual Property Bureau employee consumption cooperative printing VI. Application for patent scope 1 9 1 1 1 1 7 3 No. 6 patent application Chinese patent application scope amendments Amendment of September 27, 1994 1 · A solid electrolysis a capacitor, which is a solid electrolytic capacitor formed using a capacitor element formed of a solid electrolyte, characterized in that the etched foil used for the anode foil of the front capacitor element is at a porosity of 51% to τ 〇 2 _ a solid An electrolytic capacitor which is a solid electrolytic capacitor formed using a capacitor element formed of a solid electrolyte, characterized in that a porosity of a uranium engraved foil used for a cathode foil of the capacitor element is less than 44% 〇3. The solid electrolytic capacitor of the first aspect, wherein the porosity is 20% or more. 4. The solid electrolytic capacitor according to item 2 of the patent application, wherein the pores are above 1%. 5. The solid electrolytic capacitor according to claim 1, wherein the anode foil has a foil thickness of 70 to 180 μm. 6. The solid electrolytic capacitor of claim 2, wherein the foil of the cathode foil has a thickness of 50 to 180 μm. The solid electrolytic capacitor according to any one of claims 1 to 6, wherein the capacitor element is attached to the anode foil and the cathode foil at any position of each of the anode foil and the cathode foil, and is interposed between the anode foil and the cathode foil. There are spacers to be taken up. This paper scale applies to China National Standard (CNS) A4C (210X297 mm) — (please read the note on the back and fill out this page) Order 1264745 Ministry of Economic Affairs Intellectual Property Bureau Staff Consumer Cooperative Printed A8 B8 C8 D8 VI. The solid electrolytic capacitor according to any one of claims 1 to 6, wherein the solid electrolyte is a TCNQ complex. The solid electrolytic capacitor according to any one of claims 1 to 6, wherein the solid electrolyte is a polymer of a thiophene dielectric. 1 〇 A solid electrolytic capacitor according to claim 9, wherein the thiophene dielectric is 3,4-ethyleneoxythiophene. The solid electrolytic capacitor according to any one of claims 1 to 6, wherein the solid electrolyte is manganese dioxide. This paper size applies to the Chinese National Standard (CNS) A4 specification (210X29? mm) (please read the notes on the back and fill out this page) -2-