KR20040055882A - Method for making a aluminum condenser - Google Patents

Method for making a aluminum condenser Download PDF

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KR20040055882A
KR20040055882A KR1020020082324A KR20020082324A KR20040055882A KR 20040055882 A KR20040055882 A KR 20040055882A KR 1020020082324 A KR1020020082324 A KR 1020020082324A KR 20020082324 A KR20020082324 A KR 20020082324A KR 20040055882 A KR20040055882 A KR 20040055882A
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capacitor
electrode foil
wound
wound element
winding
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KR1020020082324A
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Korean (ko)
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장창국
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파츠닉(주)
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/15Solid electrolytic capacitors
    • H01G9/151Solid electrolytic capacitors with wound foil electrodes
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/0029Processes of manufacture

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

PURPOSE: A method is provided to significantly improve impedance and equivalent serial resistance characteristics in a high frequency by using a conductive polymer as an electrolyte for the wound element arranged in an aluminum electrolytic capacitor. CONSTITUTION: A method comprises a step of inserting a manila sheet serving as an insulating sheet(30) between an anode electrode sheet(10) and a cathode electrode sheet(20); a step of winding the anode electrode sheet, the cathode electrode sheet, and the insulating sheet into a wound element; a step of infiltrating 3-ethylenedioxythiophene and 4-ethylenedioxythiophene to the wound element; and a step of dipping the wound element into the mixture of oxidizing agent and solvent, and drying the resultant structure at a high temperature, thereby forming a conductive polymer layer on the wound element through the polymerization occurring in the etching pit of a capacitor. The wound element contains a phosphoric acid based compound so as to achieve improved withstand voltage of a conductive polyelectrolyte.

Description

알루미늄 권취형 고체전해콘덴서의 제조방법{Method for making a aluminum condenser}Manufacturing method of aluminum wound solid electrolytic capacitor {Method for making a aluminum condenser}

본 발명은 Al 고체콘덴서에 관한 것으로, 보다 상세하게는 Al 고체콘덴서에 내재되는 권취형 소자에 도전성 고분자를 전해질로 사용하여 고주파에서 임피던스 및 등가직렬저항의 특성을 크게 향상시킬 수 있는 Al 권취형 고체전해콘덴서의 제조방법에 관한 것이다.The present invention relates to an Al solid capacitor, and more particularly, an Al wound solid that can significantly improve the characteristics of impedance and equivalent series resistance at high frequencies by using a conductive polymer as an electrolyte in a wound device inherent in an Al solid capacitor. It relates to a manufacturing method of an electrolytic capacitor.

일반적으로 Al(알루미늄) 고체콘덴서는 Al을 전극으로 사용하여 대향되는 두 전극판 사이에 유전체를 개재시켜 직류전압을 인가하면 에너지(전하)를 축적하는기능을 갖는다. 상기 Al 고체콘덴서(electrolytic capacitor)는 Al박막을 이용하여 제조되며, 에칭공정, 화성공정, 절단공정, 권취공정, 함침공정, 조립공정 및 재화성공정을 통해 Al 전해콘덴서가 제조된다. 즉, 상기 Al 고체콘덴서를 구성하는 양극박(+)과 음극박(-)의 사이에는 절연막이 삽설되어 Al 고체콘덴서를 구성하는 캔에 삽입된다. 상기 Al 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 Al (aluminum) solid capacitor has a function of accumulating energy (charge) when a direct current voltage is applied through a dielectric between two opposite electrode plates using Al as an electrode. The Al solid capacitor (electrolytic capacitor) is manufactured using an Al thin film, Al 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 Al solid capacitor and inserted into a can constituting the Al solid capacitor. After the anode foil, the insulating film, and the cathode foil are inserted into the can of the Al 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)를 전해질로 이용한 콘덴서는 테트라시아노퀴노디메탄(TCNQ)의 내열성이 낮아 역시 고주파에서의 특성 대응이 어렵다는 문제점이 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 with the above-mentioned liquid electrolyte, and manganese dioxide, which is a solid electrolyte, is formed by pyrolysis of manganese nitrate, but the conductivity of manganese dioxide is low, and the capacitor using tetracyanoquinomimethane (TCNQ) as an electrolyte Tetracyanoquinomimethane (TCNQ) is low in heat resistance, there is also a problem that it is difficult to cope with the characteristics at high frequencies.

본 발명은 상기와 같은 문제점을 해결하기 위하여 안출된 것으로, 본 발명의 목적은 Al 고체콘덴서에 내재되는 권취형 소자에 도전성 고분자를 전해질로 사용하여 고주파에서 임피던스 및 등가직렬저항(ESR)의 특성을 크게 향상시킬 수 있는 Al권취형 고체전해콘덴서의 제조방법을 제공하는데 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 Al 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 Al wound solid electrolytic capacitor which can be greatly improved.

도 1은 본 발명에 따른 Al 권취형 고체전해 콘덴서의 구조를 개략적으로 나타낸 도면이다.1 is a view schematically showing the structure of an Al wound solid electrolyte 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 테이프50: roll paper tape

상기 목적을 달성하기 위하여 본 발명은 양극 전극박과 음극 전극박의 사이에 저밀도의 마닐라지로 이루어진 절연지를 삽입하여 양극 전극박과 음극 전극박 및 절연지를 함께 권취시켜 권취소자를 형성시킨 후, 상기 권취소자를 모노머로 3-에틸렌디옥시치오펜 및 4-에틸렌디옥시치오펜을 함침한 후 산화제와 용매의 혼합용액에 침적하며 일정온도의 고온에서 건조시킴으로서 콘덴서의 에칭홈의 내부까지 중합반응을 일으켜 치밀한 폴리에틸렌디옥시치오펜의 도전성 고분자층을 권취소자에 형성시켜 제조되는 것을 특징으로 하는 Al 권취형 고체전해 콘덴서의 제조방법을 제공한다.In order to achieve the above object, the present invention inserts an insulating paper made of low density manilaji between the positive electrode foil and the negative electrode foil to wind the positive electrode foil, the negative electrode foil and the insulating paper together to form a winding element, and then Impregnating the canceller with 3-ethylenedioxythiophene and 4-ethylenedioxythiophene as a monomer, and then immersed in a mixed solution of oxidizing agent and solvent and drying at a high temperature of a certain temperature to cause polymerization reaction inside the etching groove of the condenser. Provided is a method for producing an Al wound solid electrolytic capacitor, which is prepared by forming a conductive polymer layer of dense polyethylene dioxythiophene in a winding device.

본 발명에 의하면, Al 고체전해콘덴서를 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 건조시킴으로서 콘덴서의 에칭홈의 내부까지 중합반응을 일으켜 치밀한 폴리에틸렌디옥시치오펜의 도전성 고분자층을 권취소자에 형성시켜 Al 권취형 고체전해 콘덴서를 제조한다.According to the present invention, manila paper is used as the insulating paper between the positive electrode foil and the negative electrode foil constituting the Al solid electrolytic capacitor, and the positive electrode foil, the insulating paper and the negative electrode foil are wound 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. By drying at a high temperature of, a polymerization reaction is carried out to the inside of the etching groove of the capacitor to form a conductive polymer layer of dense polyethylene dioxythiophene in the winding device to produce an Al wound solid electrolyte capacitor.

이하, 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.

도 1은 본 발명에 따른 Al 권취형 고체전해 콘덴서의 구조를 개략적으로 나타낸 도면이다.1 is a view schematically showing the structure of an Al wound solid electrolyte capacitor according to the present invention.

도 1을 참조하여 Al 권취형 고체전해 콘덴서의 제조방법을 설명하면, 먼저, Al 고체콘덴서에 사용되는 전해액은 Al 고체콘덴서의 특성을 잘 구현할 수 있어야 하며, Al 고체콘덴서가 정격전압에 잘 견딜 수 있도록 하는데 많은 비중을 차지하므로 Al 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 Al wound solid electrolytic capacitor, first, the electrolyte used in the Al solid capacitor should be able to implement the characteristics of the Al solid capacitor well, the Al solid capacitor can withstand the rated voltage well. Al solid capacitors should use an electrolyte that has a high spark voltage, low resistivity, and can be used in a wide temperature range.

따라서, 알미늄 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)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 low density of manila (manila) between the aluminum anode electrode foil (10) and the cathode electrode foil (20) is used as the insulating paper (30), and then sequentially wound as a monomer to the element wound together with the lead (40). After impregnating ethylene dioxythiophene and 4-ethylene dioxythiophene, it is immersed in the mixed solution of oxidizing agent and solvent and dried at a high temperature of a certain temperature to cause polymerization reaction inside the etching pit of the condenser. A conductive polymer layer of polyethylene dioxythiophene is formed.

상기 산화제 용액으로는 파라톨루엔설폰산 제2철을 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 paratoluene sulfonic acid was used as the oxidant solution, and the mixing ratio of the monomer and the oxidant solution was selected in the range of 1:10 to 1:20, and the solvent was monovalent such as methanol, ethanol, butanol and propanol. One alcohol is selected, and the mixing ratio with the oxidizing agent is 1: 0.5 to 1: 1.

상기 전도성 고분자 전해질의 내전압을 향상시키기 위해 상기와 같이 구성된 소자에 인산계화합물을 일정한 비율을 함유시키며 침적 및 열처리 조건을 개선하였다. 상기 인산계화합물은 제일인산암모늄, 제이인산암모늄 중에서 한가지를 채택하며, 함유시키는 방법으로는 소자화시 화성액내 또는 산화제 용액에 포함시키는 방법이 있으며, 상기 두 방법이 모두 가능하다. 상기 인산화합물의 함유비율은 0.1∼3% 이내가 적당하다.In order to improve the withstand voltage of the conductive polymer electrolyte, a device containing the phosphate-based compound was contained in a predetermined ratio, and deposition and heat treatment conditions were improved. The phosphate compound is one of ammonium monophosphate and ammonium diphosphate, and the method of inclusion includes a method of incorporating it into a chemical solution or an oxidant solution during device formation, and both methods are possible. The content ratio of the phosphate compound is suitably within 0.1 to 3%.

상기의 고분자화 하는 중합 공정은 화성소자를 모노머와 산화제 용액에 순차 진공 침적 후 1차 용매의 비점보다 낮은 온도 즉 45∼70℃의 온도에서 0.5∼2시간 동안 건조하여 중합층을 형성한 후 용매로 세척 및 건조 후 재차 모노머와 산화제용액에 진공침적한다. 그리고 용매의 비점보다 높은 고온에서 즉 140∼170℃의 고온에서 0.5∼2시간 동안 건조하여 치밀하고 전도성이 강한 고분자 층을 형성시킨다.In the polymerizing polymerization process, the chemical element is sequentially vacuum deposited in a monomer and an oxidant solution, and then dried at a temperature lower than the boiling point of the primary solvent, that is, at a temperature of 45 to 70 ° C. for 0.5 to 2 hours to form a polymer layer. After rinsing and drying, vacuum immersing the monomer and the oxidant solution again And it is dried at a high temperature higher than the boiling point of the solvent, that is, 0.5 to 2 hours at a high temperature of 140 to 170 ℃ to form a dense, highly conductive polymer layer.

제품특성Product Specifications CAP(㎌)CAP TAN(%)TAN (%) LC(㎂)LC (㎂) Z(㏁)Z (㏁) ESR(㏁)ESR (㏁) 종래예(대기침적)Conventional example (atmospheric deposition) 165165 4.24.2 4848 3838 3434 실시예Example 169169 3.13.1 3232 2424 2222

(표 1)Table 1

상기 (표 1)은 제품구성 및 콘덴서의 적용예를 나타낸 것으로, 적용조건은 16V/180㎌ : 8 11.5이다.(Table 1) shows the product configuration and application examples of the capacitor, the application conditions are 16V / 180㎌: 8 11.5 to be.

진공도는 100∼650mmHg이며 유지시간은 1시간 이내로 하고, 내전압이 향상되어 16V까지 전도성고분자전해질로 확대가 가능하며, 용매는 부탄올을 사용하며, 산화제의 비율은 1 : 0.5가 되며, 중합 완료된 소자를 밀봉재와 케이스에 수납하여 콘덴서를 완성한다.Vacuum degree is 100 ~ 650mmHg, holding time is within 1 hour, and withstand voltage is improved, it can be expanded to conductive polyelectrolyte up to 16V, butanol is used as solvent, oxidizer ratio is 1: 0.5, and It is stored in the sealing material and the case to complete the condenser.

이상 설명에서 알 수 있는 바와 같이, 본 발명은 Al 고체전해콘덴서를 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 건조시킴으로서 콘덴서의 에칭홈의 내부까지 중합반응을 일으켜 치밀한 폴리에틸렌디옥시치오펜의 도전성 고분자층을 권취소자에 형성시켜 Al 권취형 고체전해 콘덴서를 제조한다.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 Al 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. By drying at a high temperature of, a polymerization reaction is carried out to the inside of the etching groove of the capacitor to form a conductive polymer layer of dense polyethylene dioxythiophene in the winding device to produce an Al wound solid electrolyte capacitor.

Claims (6)

양극 전극박과 음극 전극박의 사이에 저밀도의 마닐라지로 이루어진 절연지를 삽입하여 양극 전극박과 음극 전극박 및 절연지를 함께 권취시켜 권취소자를 형성시킨 후, 상기 권취소자를 모노머로 3-에틸렌디옥시치오펜 및 4-에틸렌디옥시치오펜을 함침한 후 산화제와 용매의 혼합용액에 침적하며 일정온도의 고온에서 건조시킴으로서 콘덴서의 에칭홈의 내부까지 중합반응을 일으켜 치밀한 폴리에틸렌디옥시치오펜의 도전성 고분자층을 권취소자에 형성시켜 제조되는 것을 특징으로 하는 Al 권취형 고체전해 콘덴서의 제조방법.After inserting an insulating paper made of low density manilaji between the positive electrode foil and the negative electrode foil, the positive electrode foil, the negative electrode foil, and the insulating paper are wound together to form a winding element, and then the winding element is 3-ethylenedioxy as a monomer. Impregnated thiophene and 4-ethylenedioxythiophene, and then immersed in a mixed solution of oxidizing agent and solvent and drying at a high temperature of a certain temperature to cause polymerization reaction inside the etching groove of the condenser. A method for producing an Al wound solid electrolytic capacitor, which is prepared by forming a layer on a winding element. 제 1 항에 있어서, 상기 산화제는 파라톨루엔설폰산 제2철을 사용하는 것을 특징으로 하는 Al 권취형 고체전해 콘덴서의 제조방법.2. The method of claim 1, wherein the oxidizing agent uses ferric paratoluene sulfonic acid. 제 1 항 또는 제 2 항에 있어서, 상기 모노머와 산화제 용액의 혼합비율은 1:10∼1:20인 것을 특징으로 하는 Al 권취형 고체전해 콘덴서의 제조방법.The method for producing an Al wound solid electrolyte capacitor according to claim 1 or 2, wherein the mixing ratio of the monomer and the oxidant solution is 1:10 to 1:20. 제 1 항에 있어서, 상기 용매는 메탄올, 에탄올, 부탄올 및 프로판올 등의 1가 알콜류 중에서 한가지를 선정하며, 산화제와의 혼합비율은 1:0.5∼1:1 인 것을 특징으로 하는 Al 권취형 고체전해 콘덴서의 제조방법.The Al winding type solid electrolyte according to claim 1, wherein the solvent is selected from monohydric alcohols such as methanol, ethanol, butanol and propanol, and the mixing ratio with the oxidizing agent is 1: 0.5 to 1: 1. Method for manufacturing a capacitor 제 1 항에 있어서, 상기 권취소자는 전도성 고분자 전해질의 내전압을 향상시키기 위해 상기와 같이 구성된 소자에 인산계화합물을 일정한 비율을 함유시켜 침적 및 열처리 조건을 개선한 것을 특징으로 하는 Al 권취형 고체전해 콘덴서의 제조방법.The Al winding type solid electrolyte according to claim 1, wherein the winding device includes a phosphate-based compound in a predetermined ratio to improve the withstand voltage of the conductive polymer electrolyte, thereby improving deposition and heat treatment conditions. Method for manufacturing a capacitor 제 5 항에 있어서, 상기 인산계화합물은 제일인산암모늄, 제이인산암모늄 중에서 한가지를 채택하고, 함유시키는 방법으로는 소자화시 화성액내 또는 산화제 용액에 포함시키며, 인산화합물의 함유비율은 0.1∼3% 인 것을 특징으로 하는 Al 권취형 고체전해 콘덴서의 제조방법.6. The method of claim 5, wherein the phosphate compound is one of ammonium monophosphate and ammonium diphosphate, and is contained in the chemical solution or in the oxidant solution during decantation, and the content of the phosphate compound is 0.1 to 3%. A method for producing an Al wound solid electrolyte capacitor, characterized in that
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