KR20060038041A - Manufacturing method of aluminum wound solid electrolytic capacitor - Google Patents
Manufacturing method of aluminum wound solid electrolytic capacitor Download PDFInfo
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- KR20060038041A KR20060038041A KR1020040087168A KR20040087168A KR20060038041A KR 20060038041 A KR20060038041 A KR 20060038041A KR 1020040087168 A KR1020040087168 A KR 1020040087168A KR 20040087168 A KR20040087168 A KR 20040087168A KR 20060038041 A KR20060038041 A KR 20060038041A
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- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
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- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
- H01G9/045—Electrodes or formation of dielectric layers thereon characterised by the material based on aluminium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-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
- H01G9/151—Solid electrolytic capacitors with wound foil electrodes
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Abstract
본 발명에 의한 알루미늄 권취형 고체 전해콘덴서의 제조방법은, 권취 소자의 고온 처리된 양극 전극박(10)의 화성 피막을 복구하기 위해 정격 전압으로 화성하는 단계와; 상기 양극 전극박과 음극 전극박의 사이에 저밀도의 마닐라지로 이루어진 절연지(30)를 삽입하여 양극 전극박(10)과 음극 전극박(20) 및 절연지를 함께 권취시킨 권취소자를 250℃의 온도에서 3시간 열처리하고 상기 절연지를 저밀도화하는 단계와; 상기 저밀도화시킨 소자를 산화제 용액인 파라톨루엔설폰산 제2철에 침적하고, 상온에서 2시간, 130℃의 고온에서 2시간 동안 순차적으로 건조시켜 전도성의 고분자 중합층을 형성하는 단계와; 단량체인 3-에틸렌디옥시치오펜 및 4-에틸렌디옥시치오펜을 메탄올과 1:3의 비율로 혼합 침적한 후 75℃에서 3시간동안 건조시켜 모노머층을 형성하는 단계와; 중합이 완료된 소자를 밀봉재와 케이스에 수납 조립하는 단계와; 상기 조립된 콘덴서를 에이징하는 단계를 포함하는 것을 특징으로 한다. 이와 같은 본 발명은 알루미늄 고체 콘덴서에 내재되어 있는 권취형 소자에 도전성 고분자를 전해질로 사용한 콘덴서로 제품의 쇼트 불량이 저감될 뿐만 아니라 고주파(100∼300㎑)에서 임피던스 및 등가직렬저항(E.S.R) 특성이 뛰어난 효과가 있다. The method for manufacturing an aluminum wound solid electrolytic capacitor according to the present invention comprises the steps of: forming at a rated voltage to recover a chemical conversion film of the cathode electrode foil 10 subjected to the high temperature treatment of the winding element; Between the positive electrode foil and the negative electrode foil was inserted an insulating paper 30 made of low density manilaji winding the positive electrode electrode 10, the negative electrode foil 20 and the insulating paper wound together at a temperature of 250 ℃ Heat-treating for 3 hours to reduce the density of the insulating paper; Immersing the low-density device in ferric paratoluenesulfonic acid, which is an oxidizing agent solution, and sequentially drying the mixture for 2 hours at room temperature and 2 hours at a high temperature of 130 ° C. to form a conductive polymer polymerization layer; Mixing and depositing monomers of 3-ethylenedioxythiophene and 4-ethylenedioxythiophene in a ratio of 1: 3 with methanol and drying at 75 ° C. for 3 hours to form a monomer layer; Storing and assembling the polymerized element into a sealing member and a case; It characterized in that it comprises the step of aging the assembled capacitor. As described above, the present invention is a capacitor using a conductive polymer as an electrolyte in a winding type device inherent in an aluminum solid capacitor, which not only reduces short defects of the product but also exhibits impedance and equivalent series resistance (ESR) characteristics at a high frequency (100 to 300 kHz). This has an excellent effect.
Description
도 1은 본 발명에 따른 알루미늄 권취형 고체 전해콘덴서의 구조를 개략적으로 나타낸 도면이다. 1 is a view schematically showing the structure of an aluminum wound solid electrolytic capacitor according to the present invention.
<도면의 주요부분에 대한 부호의 간단한 설명><Brief description of symbols for the main parts of the drawings>
10 : 양극 전극박 20 : 음극 전극박10: anode electrode foil 20: cathode electrode foil
30 : 절연지 40 : 리이드30: insulating paper 40: lead
50 : 권지 테이프 50: roll paper tape
본 발명은 알루미늄 권취형 고체 전해콘덴서의 제조 방법에 관한 것으로, 보다 상세하게는, 알루미늄 고체 콘덴서에 내재되어 있는 권취형 소자에 도전성 고분자를 전해질로 사용한 콘덴서로 고주파(100∼300㎑)에서 임피던스 및 등가직렬저항(E.S.R) 특성이 뛰어난 알루미늄 권취형 고체 전해콘덴서의 제조방법에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing an aluminum wound solid electrolytic capacitor. More specifically, the present invention relates to a winding type device inherent in an aluminum solid capacitor. The present invention relates to a method for producing an aluminum wound solid electrolytic capacitor having excellent equivalent series resistance (ESR) characteristics.
일반적으로, 알루미늄 고체 전해콘덴서는 알루미늄을 전극으로 사용하여 대 향되는 두 전극판 사이에 유전체를 개재시켜 직류전압을 인가하면 에너지(전하)를 축적하는 기능을 갖는다. 상기 알루미늄 고체콘덴서(electrolytic capacitor)는 알루미늄박막을 이용하여 제조되며, 에칭공정, 화성공정, 절단공정, 권취공정, 함침공정, 조립공정 및 재화성공정을 통해 알루미늄 전해콘덴서가 제조된다. 즉, 상기 알루미늄 고체콘덴서를 구성하는 양극박(+)과 음극박(-)의 사이에는 절연막이 삽설되어 알루미늄 고체콘덴서를 구성하는 캔에 삽입된다. 상기 알루미늄 고체콘덴서의 캔에 양극박, 절연막, 및 음극박을 삽입한 후 캔의 내부에 전해액을 주입하게 된다. 상기 전해액은 여러가지 화공약품을 조성해서 만든 액체로서 실질적인 음극역할을 한다. In general, an aluminum solid electrolytic capacitor has a function of accumulating energy (charge) when a direct current voltage is applied through a dielectric between two opposite electrode plates using aluminum as an electrode. The aluminum solid capacitor is manufactured using an aluminum thin film, and an aluminum electrolytic capacitor is manufactured through an etching process, a chemical conversion process, a cutting process, a winding process, an impregnation process, an assembly process, and a regeneration process. That is, an insulating film is inserted between the positive electrode foil (+) and the negative electrode foil (-) constituting the aluminum solid capacitor and inserted into a can constituting the aluminum solid capacitor. After the anode foil, the insulating film, and the cathode foil are inserted into the can of the aluminum solid capacitor, the electrolyte is injected into the can. The electrolyte is a liquid made by forming various chemicals and serves as a substantial cathode.
최근에는 전자기기의 디지털화 및 고주파화에 따라 알루미늄 고체콘덴서는 소형 대용량으로 고주파 영역에서 저항이 낮은 것을 요구하고 있다. 그런데 종래의 전해질로는 에틸렌글리콜(EG) 또는 감마부틸락토(GBL) 등의 용매에 4급염을 용해한 액체 전해액과, 이산화망간 또는 테트라시아노퀴노디메탄(TCNQ) 등의 고체 전해액이 있다. 상기의 액체 전해액으로는 저항이 높아 고주파에서의 대응이 어렵고, 또한 고체 전해액인 이산화망간은 질산망간의 열분해에 의해 형성되나 이산화망간의 전도도가 낮고, 테트라시아노퀴노디메탄(TCNQ)을 전해질로 이용한 콘덴서는 테트라시아노퀴노디메탄(TCNQ)의 내열성이 낮아 역시 고주파에서의 특성 대응이 어렵다는 결점이 있다. Recently, with the digitization and high frequency of electronic devices, aluminum solid capacitors are required to have low resistance in the high frequency region with a small capacity. However, conventional electrolytes include liquid electrolytes in which quaternary salts are dissolved in a solvent such as ethylene glycol (EG) or gamma butyl lactose (GBL), and solid electrolyte solutions such as manganese dioxide or tetracyanoquinomimethane (TCNQ). It is difficult to cope at high frequency because the liquid electrolyte solution is high, and manganese dioxide, which is a solid electrolyte, is formed by thermal decomposition of manganese nitrate, but the conductivity of manganese dioxide is low, and a capacitor using tetracyanoquinomimethane (TCNQ) as an electrolyte. Tetracyanoquinomethane (TCNQ) has a disadvantage in that it is difficult to cope with characteristics at high frequencies because of its low heat resistance.
본 발명은 상기와 같은 문제점을 해결하기 위하여 안출된 것으로, 본 발명의 목적은 알루미늄 고체콘덴서에 내재되는 권취형 소자에 도전성 고분자를 전해질로 사용하여 고주파에서 임피던스 및 등가직렬저항(ESR)의 특성을 크게 향상시킬 수 있는 알루미늄 권취형 고체 전해콘덴서의 제조방법을 제공하는 데 있다.The present invention has been made to solve the above problems, and an object of the present invention is to use the conductive polymer as an electrolyte in a wound device inherent in an aluminum solid capacitor to improve the characteristics of impedance and equivalent series resistance (ESR) at high frequencies. An object of the present invention is to provide a method for manufacturing an aluminum wound solid electrolytic capacitor which can be greatly improved.
상기한 목적을 달성하기 위한 본 발명에 의한 알루미늄 권취형 고체 전해콘덴서의 제조방법에 있어서, 권취 소자의 고온 처리된 양극 전극박의 화성 피막을 복구하기 위해 정격 전압으로 화성하는 단계와; 상기 양극 전극박과 음극 전극박의 사이에 저밀도의 마닐라지로 이루어진 절연지를 삽입하여 양극 전극박과 음극 전극박 및 절연지를 함께 권취시킨 권취소자를 250℃의 온도에서 3시간 열처리하고 상기 절연지를 저밀도화하는 단계와; 상기 저밀도화시킨 소자를 산화제 용액인 파라톨루엔설폰산 제2철에 침적하고, 상온에서 2시간, 130℃의 고온에서 2시간 동안 순차적으로 건조시켜 전도성의 고분자 중합층을 형성하는 단계와; 단량체인 3-에틸렌디옥시치오펜 및 4-에틸렌디옥시치오펜을 메탄올과 1:3의 비율로 혼합 침적한 후 75℃에서 3시간동안 건조시켜 모노머층을 형성하는 단계와; 중합이 완료된 소자를 밀봉재와 케이스에 수납 조립하는 단계와; 상기 조립된 콘덴서를 에이징하는 단계를 포함하는 것을 특징으로 한다.A method of manufacturing an aluminum wound solid electrolytic capacitor according to the present invention for achieving the above object, comprising the steps of: forming at a rated voltage to recover a chemical conversion film of a high-temperature treated cathode electrode foil of a winding element; Between the positive electrode foil and the negative electrode foil, an insulating paper made of low density manila paper was inserted, and the winding element wound together with the positive electrode foil, the negative electrode foil, and the insulating paper was heat treated at a temperature of 250 ° C. for 3 hours to reduce the density of the insulating paper. Making a step; Immersing the low-density device in ferric paratoluenesulfonic acid, which is an oxidizing agent solution, and sequentially drying the mixture for 2 hours at room temperature and 2 hours at a high temperature of 130 ° C. to form a conductive polymer polymerization layer; Mixing and depositing monomers of 3-ethylenedioxythiophene and 4-ethylenedioxythiophene in a ratio of 1: 3 with methanol and drying at 75 ° C. for 3 hours to form a monomer layer; Storing and assembling the polymerized element into a sealing member and a case; It characterized in that it comprises the step of aging the assembled capacitor.
이하, 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
도 1은 본 발명에 따른 알루미늄 권취형 고체전해 콘덴서의 구조를 개략적으로 나타낸 도면이다.1 is a view schematically showing the structure of an aluminum wound solid electrolyte capacitor according to the present invention.
본 발명에 의하면, 알루미늄 고체 전해콘덴서를 구성하는 알루미늄 양극 전 극박과 음극 전극박의 사이에 저밀도의 마닐라지를 절연지로 사용하고, 상기 양극 전극박과 절연지 및 음극 전극박을 함께 권취시킨다. 상기 양극 전극박과 절연지 및 음극 전극박을 함께 권취시켜 형성된 권취소자에 단량체로 3-에틸렌디옥시치오펜 및 4-에틸렌디옥시치오펜과 산화제 용액을 함침시켜 도전성 고분자 전해질층을 형성시키는 공정에 관한 것으로, 산화 피막 표면 및 콘덴서의 에칭홈의 내부까지 중합반응을 일으켜 치밀한 폴리에틸렌디옥시치오펜의 도전성 고분자층을 형성하기 위한 공정 순서는 다음과 같다. According to the present invention, low-density manila is used as the insulating paper between the aluminum anode electrode foil and the cathode electrode foil constituting the aluminum solid electrolytic capacitor, and the cathode electrode foil, the insulation paper and the cathode electrode foil are wound together. In the step of forming a conductive polymer electrolyte layer by impregnating 3-ethylene dioxythiophene, 4-ethylene dioxythiophene and an oxidizing agent solution in the winding device formed by winding the positive electrode foil, insulating paper and negative electrode foil together In this regard, the process sequence for the polymerization reaction to the surface of the oxide film and the inside of the etching groove of the capacitor to form a dense polyethylene dioxythiophene conductive polymer layer is as follows.
도1을 참조하여 알루미늄 권취형 고체 전해콘덴서의 제조방법을 설명하면, 먼저, 알루미늄 고체콘덴서에 사용되는 전해액은 알루미늄 고체콘덴서의 특성을 잘 구현할 수 있어야 하며, 알루미늄 고체콘덴서가 정격전압에 잘 견딜 수 있도록 하는데 많은 비중을 차지하므로 알루미늄 고체콘덴서는 스파크전압(spark voltage)값이 높아지고, 낮은 비저항값을 갖으며, 넓은 온도범위에서 사용할 수 있는 전해액을 사용해야 한다. Referring to Figure 1 describes the manufacturing method of the aluminum wound solid electrolytic capacitor, first, the electrolyte used in the aluminum solid capacitor should be able to implement the characteristics of the aluminum solid capacitor well, the aluminum solid capacitor can withstand the rated voltage well. Aluminum solid capacitors must use an electrolyte that has high spark voltage, low resistivity, and can be used in a wide temperature range.
따라서, 알루미늄 양극 전극박(10)과 음극 전극박(20)의 사이에 저밀도의 마닐라지(manila)를 절연지(30)로 하여 리이드(40)와 함께 권취시킨 소자에 순차적으로 모노머(monomer;단량체(單量體))로 3-에틸렌디옥시치오펜 및 4-에틸렌디옥시치오펜을 함침한 후 산화제와 용매의 혼합용액에 침적하며 일정온도의 고온에서 건조시킴으로서 콘덴서의 에칭홈(etching pit)의 내부까지 중합반응을 일으켜 치밀한 폴리에틸렌디옥시치오펜의 도전성 고분자층을 형성시킨다.Therefore, a monomer (monomer) is sequentially added to the element wound together with the
상기 산화제 용액으로는 파라톨루엔설폰산 제2철을 부탄올 용매에 30∼50% 희석하여 사용하였으며, 모노머와 산화제 용액의 혼합비율은 1:10∼1:20의 범위에서 선정하였으며, 용매는 메탄올, 에탄올, 부탄올 및 프로판올 등의 1가 알콜류 중에서 한가지를 선정하며, 산화제와의 혼합비율은 1:0.5∼1:1로 한다.Ferric paratoluenesulfonic acid was diluted by 30 to 50% in a butanol solvent as the oxidant solution. The mixing ratio of monomer and oxidant solution was selected in the range of 1:10 to 1:20, and the solvent was methanol, One of the monohydric alcohols such as ethanol, butanol and propanol is selected, and the mixing ratio with the oxidizing agent is 1: 0.5 to 1: 1.
본 발명의 제일실시예에 있어서, 고분자화하는 중합 공정은 권취된 소자를 먼저 화성을 실시한 후, 순수에 세척하고, 200∼280℃의 고온에서 10분∼3시간 열처리하여 절연지를 저밀도화하고, 상기 저밀도화시킨 소자를 산화제 용액에 침적 후, 모노머 즉, 단량체를 메탄올, 에탄올, 부탄올 등의 1가 알콜류의 용매에 1:1∼1:5의 비율(무게비)로 혼합한 용액에 침적시킨다. 여기서 산화제 침적 건조는 상온∼100℃의 온도 범위에서 1∼3시간 실시하며, 단량체 용액 침적 건조는 상온에서 30분∼3시간, 50∼120℃의 온도에서 1∼5시간동안 1, 2차에 걸쳐 실시하여 치밀한 중합층을 형성한다. 상기한 2차 건조시의 온도 및 시간은 단량체에 혼합되는 용매의 비점을 고려하여 설정하였다. 중합 완료된 소자를 밀봉재와 케이스에 수납하여 에이징 처리하고 콘덴서를 완성하였다.In the first embodiment of the present invention, in the polymerization step of polymerizing, the wound element is first converted into chemicals, washed with pure water, heat treated at a high temperature of 200 to 280 ° C for 10 minutes to 3 hours, and the insulation paper is made low in density. The low-density device is immersed in an oxidizing agent solution, and then immersed in a solution in which a monomer, that is, monomer, is mixed in a solvent (a weight ratio) of 1: 1 to 1: 5 in a solvent of a monohydric alcohol such as methanol, ethanol or butanol. The oxidant deposition drying is carried out for 1 to 3 hours in the temperature range of room temperature to 100 ° C, and the monomer solution deposition drying is carried out for 1 to 5 hours at a temperature of 30 minutes to 3 hours and 50 to 120 ° C at room temperature. It performs over and forms a dense polymer layer. The temperature and time at the time of secondary drying were set in consideration of the boiling point of the solvent mixed with the monomer. The polymerized device was housed in a sealing material and a case, aged, and a condenser was completed.
(표1)Table 1
상기한 표1은 제품구성 및 콘덴서의 적용예를 나타낸 것으로, 적용조건은 16V/39㎌ : 6.3ψ×6ι이다.Table 1 above shows the product configuration and application examples of the capacitor, and the application conditions are 16V / 39㎌: 6.3ψ × 6ι.
상기한 실시예 1은 모노머층을 형성하는 단계에서 단량체인 3-에틸렌디옥시치오펜 및 4-에틸렌디옥시치오펜을 메탄올과 1:3의 비율로 혼합 침적한 후 75℃에 서 3시간동안 건조시키는 것에 따른 시험 결과이고, 상기 실시예 2는 모노머층을 형성하는 단계에서 단량체인 3-에틸렌디옥시치오펜 및 4-에틸렌디옥시치오펜을 메탄올과 1:3의 비율로 혼합 침적한 후 120℃에서 3시간동안 건조시키는 것에 따른 시험 결과이다.In Example 1, a monomer layer of 3-ethylenedioxythiophene and 4-ethylenedioxythiophene was mixed and deposited in a ratio of 1: 3 with methanol in a step of forming a monomer layer at 75 ° C. for 3 hours. The test result according to the drying, Example 2 after mixing and depositing the monomer 3-ethylene dioxythiophene and 4-ethylene dioxythiophene in a ratio of 1: 3 with methanol in the step of forming a monomer layer It is the test result by drying at 120 degreeC for 3 hours.
이상 설명에서 알 수 있는 바와 같이, 본 발명은 알루미늄 고체 전해콘덴서를 구성하는 양극 전극박과 음극 전극박의 사이에 절연지로 마닐라지를 사용하고, 상기 양극 전극박과 절연지 및 음극 전극박을 함께 권취시킨다. 상기 양극 전극박과 절연지 및 음극 전극박을 함께 권취시켜 형성된 권취소자는 모노머로 3-에틸렌디옥시치오펜 및 4-에틸렌디옥시치오펜을 함침한 후 산화제와 용매의 혼합용액에 침적하며 일정온도의 고온에서 건조시키고, 콘덴서의 에칭홈의 내부까지 중합반응을 일으켜 치밀한 폴리에틸렌디옥시치오펜의 도전성 고분자층을 권취소자에 형성시켜 알루미늄 권취형 고체전해 콘덴서를 제조함으로써, 알루미늄 고체 콘덴서에 내재되어 있는 권취형 소자에 도전성 고분자를 전해질로 사용한 콘덴서로 제품의 쇼트 불량이 저감될 뿐만 아니라 고주파(100∼300㎑)에서 임피던스 및 등가직렬저항(E.S.R) 특성이 뛰어난 효과가 있다.
As can be seen from the above description, the present invention uses manila paper as an insulating paper between the positive electrode foil and the negative electrode foil constituting the aluminum solid electrolytic capacitor, and winds the positive electrode foil, the insulating paper and the negative electrode foil together. . The winding device formed by winding the positive electrode foil, the insulating paper, and the negative electrode foil together is impregnated with 3-ethylenedioxythiophene and 4-ethylenedioxythiophene as a monomer, and then immersed in a mixed solution of an oxidizing agent and a solvent and having a predetermined temperature. It is dried at a high temperature, and a polymerization reaction is carried out to the inside of the etching groove of the capacitor to form an electroconductive polymer layer of dense polyethylene dioxythiophene in the winding element to produce an aluminum wound solid electrolyte capacitor, which is inherent in the aluminum solid capacitor. As a capacitor using a conductive polymer as an electrolyte in a wound device, short-circuit defects of the product are not only reduced, but also excellent in impedance and equivalent series resistance (ESR) characteristics at high frequencies (100 to 300 kHz).
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