KR20040055881A - Method for making a aluminum condenser - Google Patents
Method for making a aluminum condenser Download PDFInfo
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- KR20040055881A KR20040055881A KR1020020082323A KR20020082323A KR20040055881A KR 20040055881 A KR20040055881 A KR 20040055881A KR 1020020082323 A KR1020020082323 A KR 1020020082323A KR 20020082323 A KR20020082323 A KR 20020082323A KR 20040055881 A KR20040055881 A KR 20040055881A
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- solvent
- electrode foil
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- capacitor
- oxidizing agent
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- 238000000034 method Methods 0.000 title claims abstract description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 title abstract description 5
- 239000003990 capacitor Substances 0.000 claims abstract description 36
- 239000007800 oxidant agent Substances 0.000 claims abstract description 18
- 238000004804 winding Methods 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 12
- 229920001940 conductive polymer Polymers 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 9
- 238000005530 etching Methods 0.000 claims abstract description 7
- YMMGRPLNZPTZBS-UHFFFAOYSA-N 2,3-dihydrothieno[2,3-b][1,4]dioxine Chemical compound O1CCOC2=C1C=CS2 YMMGRPLNZPTZBS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229920000642 polymer Polymers 0.000 claims abstract description 5
- 239000011888 foil Substances 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 20
- 239000007784 solid electrolyte Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims 2
- 150000001298 alcohols Chemical class 0.000 claims 1
- 229930192474 thiophene Natural products 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 8
- GKWLILHTTGWKLQ-UHFFFAOYSA-N 2,3-dihydrothieno[3,4-b][1,4]dioxine Chemical compound O1CCOC2=CSC=C21 GKWLILHTTGWKLQ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005406 washing Methods 0.000 abstract description 2
- 238000007598 dipping method Methods 0.000 abstract 3
- 239000000203 mixture Substances 0.000 abstract 1
- 230000002794 monomerizing effect Effects 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 6
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 4
- 239000010408 film Substances 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LDVVMCZRFWMZSG-OLQVQODUSA-N (3ar,7as)-2-(trichloromethylsulfanyl)-3a,4,7,7a-tetrahydroisoindole-1,3-dione Chemical compound C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)Cl)C(=O)[C@H]21 LDVVMCZRFWMZSG-OLQVQODUSA-N 0.000 description 1
- 239000005745 Captan Substances 0.000 description 1
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 1
- 229940117949 captan Drugs 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229940021013 electrolyte solution Drugs 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000008101 lactose Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- H01G9/0029—Processes of manufacture
-
- 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
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
- H01G9/035—Liquid electrolytes, e.g. impregnating materials
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
Description
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 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)(Short description of symbols for main parts of drawing)
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.
고분자화 하는 중합 공정은 권취소자를 모노머와 산화제 용액에 순차 진공 침적후 1차 용매의 비점보다 낮은 온도 즉 45∼70℃에서 0.5∼2시간동안 건조하여 중합층을 형성하고 용매로 세척 및 건조 후 재차 모노머와 산화제용액에 진공 침적한다. 그리고 용매의 비점보다 높은 고온에서 즉, 140∼170℃의 온도에서 0.5∼2시간동안 건조하여 치밀하고 전도성이 강한 고분자 층을 형성시킨다.In the polymerization process to polymerize, the winding device is sequentially vacuum deposited on the monomer and the 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, followed by washing and drying with a solvent. Again vacuum immersed in monomer and oxidant solution. 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 temperature of 140 to 170 ℃ to form a dense, highly conductive polymer layer.
(표 1)Table 1
상기 (표 1)은 제품구성 및 콘덴서의 적용예를 나타낸 것으로, 적용조건은 10V/330㎌ : 10 12.5이다.(Table 1) shows the product configuration and application examples of the capacitor, the application conditions are 10V / 330㎌: 10 12.5 to be.
진공도는 100∼650mmHg이며 유지시간은 1시간 이내로 한다. 중합 완료된 소자를 밀봉재와 케이스에 수납하여 콘덴서를 완성한다.The degree of vacuum is 100-650 mmHg and the holding time is within 1 hour. The polymerized element is stored in a sealing material and a case to complete a capacitor.
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.
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