KR20040019478A - Electrolyte For Aluminium Electrolysis Capacitor And Aluminium Electrolysis Capacitor Having the Same - Google Patents
Electrolyte For Aluminium Electrolysis Capacitor And Aluminium Electrolysis Capacitor Having the Same Download PDFInfo
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- KR20040019478A KR20040019478A KR1020020051019A KR20020051019A KR20040019478A KR 20040019478 A KR20040019478 A KR 20040019478A KR 1020020051019 A KR1020020051019 A KR 1020020051019A KR 20020051019 A KR20020051019 A KR 20020051019A KR 20040019478 A KR20040019478 A KR 20040019478A
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- electrolyte
- electrolytic capacitor
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- ethylene glycol
- acid
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 50
- 239000003990 capacitor Substances 0.000 title claims abstract description 41
- 229910052782 aluminium Inorganic materials 0.000 title claims description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 23
- 239000004411 aluminium Substances 0.000 title 2
- 238000005868 electrolysis reaction Methods 0.000 title 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 51
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 7
- 239000008151 electrolyte solution Substances 0.000 claims description 28
- 150000001412 amines Chemical class 0.000 claims description 14
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 230000014509 gene expression Effects 0.000 abstract 2
- -1 amine salt Chemical class 0.000 abstract 1
- 239000000047 product Substances 0.000 description 15
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 239000004327 boric acid Substances 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 230000003111 delayed effect Effects 0.000 description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 229930195725 Mannitol Natural products 0.000 description 2
- 241000220317 Rosa Species 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000009499 grossing Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000594 mannitol Substances 0.000 description 2
- 235000010355 mannitol Nutrition 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 2
- 229940086542 triethylamine Drugs 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- SATJMZAWJRWBRX-UHFFFAOYSA-N azane;decanedioic acid Chemical compound [NH4+].[NH4+].[O-]C(=O)CCCCCCCCC([O-])=O SATJMZAWJRWBRX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 125000005619 boric acid group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000000866 electrolytic etching Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000008646 thermal stress Effects 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
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
- H01G9/035—Liquid electrolytes, e.g. impregnating materials
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
Description
본 발명은 내열성이 우수한 알루미늄 전해 콘덴서용 전해액 및 이를 포함하는 알루미늄 전해 콘덴서에 관한 것이며, 보다 상세하게는 아민류를 사용함으로써 전해질의 부반응이 억제되는 내열성이 우수한 알루미늄 전해 콘덴서용 전해액 및 이를 포함하는 중,고압용 알루미늄 전해 콘덴서에 관한 것이다.The present invention relates to an electrolytic solution for aluminum electrolytic capacitors having excellent heat resistance and an aluminum electrolytic capacitor comprising the same, and more particularly, to an aluminum electrolytic capacitor electrolyte solution having excellent heat resistance in which side reactions of electrolytes are suppressed by using amines, It relates to an aluminum electrolytic capacitor for high pressure.
알루미늄 전해 콘덴서는 고순도의 알루미늄박의 표면을 전해 에칭 방식으로 표면적을 확대시킨 후 붕산수용액 등에서 화성(양극산화)시켜 절연성 산화피막 (Al2O3)이 형성된 변금속을 양극전극으로 사용하고, 산화피막층을 유전체로 하여, 이 산화피막층의 표면을 전해질층으로 작용하는 전해액과 접촉시키고, 통상 음극으로 칭하여지는 집전용 전극을 배치하여 구성된다.The aluminum electrolytic capacitor expands the surface area of high-purity aluminum foil by electrolytic etching method, and then chemically converts it (anodizes) in an aqueous solution of boric acid, and uses a modified metal having an insulating oxide film (Al 2 O 3 ) as an anode electrode. It is comprised by making a coating layer into a dielectric material, making the surface of this oxide film layer contact with the electrolyte solution which acts as an electrolyte layer, and arrange | positioning the collector electrode normally called a cathode.
여기서 전해 콘덴서의 전해액은 주로 에틸렌글리콜, 아디피산, 붕산, 암모늄염 등의 이온 전도성 혼합액이며 유전체의 산화피막층에 직접 접촉하여 실질적인 음극의 역할을 한다. 즉, 전해액은 전해 콘덴서의 유전체와 집전 음극과의 사이에 개재되며, 따라서, 전해액의 저항분이 전해 콘덴서에 직렬로 삽입되어 ESR(등가직렬저항)을 구성하게 되므로, 전해액의 특성이 리플발열이나 tan δ값등의 전해콘덴서의 특성을 좌우하는 큰 요인으로 작용한다.The electrolytic solution of the electrolytic capacitor is mainly an ion conductive mixed solution of ethylene glycol, adipic acid, boric acid, ammonium salt, etc., and acts as a substantial cathode by directly contacting the oxide film layer of the dielectric. That is, the electrolyte is interposed between the dielectric of the electrolytic capacitor and the current collector cathode. Therefore, the resistance of the electrolyte is inserted in series into the electrolytic capacitor to form an ESR (equivalent series resistance). It acts as a big factor in determining the characteristics of electrolytic capacitors such as δ value.
종래 전해 콘덴서중, 화성 과정시 인가하는 전압인 불꽃 전압이 비교적 높은 중·고압용 전해액에는 에틸렌 글리콜을 용매로 그리고 세바신산, 아젤라인산등의 유기 디카르복시산 또는 그 염이 용질로 사용되었다. 그러나, 이들 용질은 용해도가 작아 저온에서 결정으로 석출되기 쉽기 때문에 콘덴서의 저온특성이 저하되는 문제가 있다.In the conventional electrolytic capacitors, ethylene glycol is used as a solvent, and organic dicarboxylic acids such as sebacic acid and azelaic acid, or salts thereof, are used as a solute in a medium-high pressure electrolyte having a relatively high spark voltage applied during the chemical conversion process. However, since these solutes have low solubility and are liable to precipitate into crystals at low temperatures, there is a problem that the low temperature characteristics of the condenser are lowered.
또한, 일본 특허공보 제 60-13296호에는 1,6-부틸 옥탄이산(二酸) 또는 그의 암모늄염을 용질로 이용한 전해액 그리고 일본 특허공보 제 63-15738호에는 5,6-도데칸이산(二酸) 또는 그의 암모늄염을 용질로 이용한 전해액이 개시되어 있다. 이러한 이염기산 또는 그 염을 이용한 전해액은 불꽃 전압 및 전도도가 높고, 용해성 또한 크기 때문에 양호한 저온 특성을 나타낸다.Further, Japanese Patent Publication No. 60-13296 discloses an electrolytic solution using 1,6-butyl octane diacid or its ammonium salt as a solute, and Japanese Patent Publication No. 63-15738 discloses 5,6-dodecane diacid. Or an ammonium salt thereof as a solute. The electrolyte solution using such dibasic acid or salt thereof shows good low temperature characteristics because of high spark voltage and conductivity, and high solubility.
그러나, 상기 전해액은 125℃이상의 온도에서는 1차적으로 에틸렌 글리콜의 수산기와 용질의 카르복시기 사이의 에스테르화 반응으로 인하여 이온이 감소되고 이온감소로 인하여 전도도가 저하된다. 또한, 장시간동안 고온에 방치하면 부반응으로서 전해질 분자내에서 탈수 축합반응이 일어나 전해질 부산물인 아미드가 생성됨으로 전해액의 성능이 급격하게 열화되고, 전극이 부식되며, 제품의 ESR증대, 내전압 강하, 쇼트 폭파등의 고장발생의 원인이 된다. 따라서, 현재 일반적으로 그 사용온도 범위가 105℃로 제한되며, 125℃이상의 고온 보증 제품에 적용하기에는 그 수명특성이 충분하지 않은 문제가 있다.However, the electrolyte has a decrease in ions due to esterification reaction between hydroxyl group of ethylene glycol and carboxyl group of solute at temperature of 125 ° C or higher, and conductivity decreases due to ion reduction. In addition, if left at high temperature for a long time, the dehydration condensation reaction occurs in the electrolyte molecule as a side reaction, resulting in the formation of amide, an electrolyte by-product, which rapidly degrades the performance of the electrolyte, corrodes the electrode, increases the ESR of the product, lowers the breakdown voltage, and blows the shot. This can cause a malfunction. Therefore, the current temperature range is generally limited to 105 ℃, there is a problem that its life characteristics are not sufficient to apply to high temperature assurance products of 125 ℃ or more.
또한, 최근 스위칭 전원을 사용한 전자기기 즉, 아답타, 휴대폰 충전기, 회로 수납형 전구(일명 장미전구)등이 일반 가정에서 보편적으로 사용됨으로써, 알루미늄 전해 콘덴서의 안정성에 대한 요구가 높아지고 있다.In addition, recently, electronic devices using a switching power supply, such as an adapter, a mobile phone charger, a circuit accommodating light bulb (aka rose light bulb), and the like are commonly used in general homes, thereby increasing the demand for stability of aluminum electrolytic capacitors.
즉, 최근 소형 전원 평활용 전해 콘덴서가 이용되고 있는 아답타, 휴대용 충전기, 회로 수납형 전구(일명 장미전구)등에서는 콘덴서를 제품세트내의 밀폐공간에 삽입하여 사용한다. 그러나, 사용시 주위 사용온도의 상승으로 인하여 전해 콘덴서의 방열이 지연된다. 또한, 수납 공간 부족으로 인한 저용량 전해 콘덴서를 사용하게 됨으로 이로 인하여 리플 내부 발열의 증대로 인한 고장 발생율이 문제시 된다. 이와 같은 문제는 제품내에서 구동되는 실질적인 음극인 전해액의 보다 높은 내열성 유무에 기인한 것일 뿐만 아니라, 또한, 이상전압 인가에 따른 내폭파 안정성 및 교류 부하의 증대로 인하여 제품에 가하여지는 열적 스트레스에 따른 콘덴서의 고온 내열성의 확보등이 요구된다.In other words, adapters, portable chargers, and circuit-type light bulbs (also called rose bulbs), which have been recently used for small power supply smoothing electrolytic capacitors, are used by inserting the capacitors into a sealed space in a product set. However, during use, the heat dissipation of the electrolytic capacitor is delayed due to the increase in the ambient operating temperature. In addition, the use of low-capacity electrolytic capacitors due to lack of storage space is a problem caused by the failure rate due to the increase in the internal heat generated in the ripple. This problem is not only caused by the presence or absence of higher heat resistance of the electrolyte, which is a substantially negative electrode driven in the product, but also by the thermal stress applied to the product due to the explosion resistance stability and the increase of the AC load due to the application of an abnormal voltage. It is required to ensure high temperature heat resistance of the capacitor.
전해 콘덴서의 이러한 내열성을 증대시키기 위해 전해액의 보다 우수한 고온 안정성의 확보, 저비저항화 및 우수한 재화성능이 요구된다.In order to increase such heat resistance of the electrolytic capacitor, it is required to ensure better high temperature stability of the electrolyte solution, lower specific resistance, and excellent material performance.
이에 본 발명의 목적은 고온에서 전해질의 부가반응을 억제함으로써 내열성이 우수한 중, 고압용 알루미늄 전해 콘덴서용 전해액 및 이를 이용한 중, 고압용 알루미늄 전해콘덴서를 제공하는 것이다.Accordingly, an object of the present invention is to provide a medium and high pressure aluminum electrolytic capacitor electrolyte having excellent heat resistance by suppressing the addition reaction of the electrolyte at a high temperature and a medium and high pressure aluminum electrolytic capacitor using the same.
본 발명의 다른 목적은 전해액의 비저항을 충분히 낮게 유지함으로써 교류 전원으로 인한 내부발열분이 적고, 고온 안정성 및 내 리플발열특성이 우수하며, 적정한 화성성이 부여되는 1차 전원 평활능력이 우수한 중, 고압용 알루미늄 전해 콘덴서용 구동용 전해액 및 이를 이용한 알루미늄 전해 콘덴서에 관한 것이다.Another object of the present invention is to maintain the specific resistance of the electrolyte sufficiently low, low internal heating content due to AC power, excellent high temperature stability and ripple heat-resisting characteristics, medium and high pressure excellent in the primary power smoothing ability is given the appropriate chemical composition The present invention relates to a driving electrolyte for an aluminum electrolytic capacitor and an aluminum electrolytic capacitor using the same.
본 발명에 일 견지에 의하면,According to one aspect of the present invention,
당량비(산의 당량/염기의 당량)가 1∼2로된 하나 또는 그 이상의 화학식 HOOC-(CH2)n-COOH (n = 2∼10)의 유기 디카르복시산과 하나 또는 그 이상의 화학식 ((CH2)a(CH3))bNH3-b(a=0∼3, b=1∼3)의 아민 염기로 구성되는 전해질 10∼35중량%,One or more organic dicarboxylic acids of the equivalent ratio (equivalent of acid / equivalent to base) of 1 to 2, with one or more of organic dicarboxylic acids of formula HOOC- (CH 2 ) n -COOH (n = 2 to 10) 2 ) 10 to 35% by weight of an electrolyte consisting of an amine base of a (CH 3 )) b NH 3-b (a = 0 to 3, b = 1 to 3),
에틸렌 글리콜, 디에틸렌 글리콜 및 이들의 혼합물로 구성되는 그룹으로 부터 선택된 용매 60∼85중량% 및60 to 85% by weight of a solvent selected from the group consisting of ethylene glycol, diethylene glycol and mixtures thereof
수분 3∼7중량%,Moisture 3-7% by weight,
를 포함하여 이루어지는 알루미늄 전해 콘덴서용 전해액이 제공된다.There is provided an electrolytic solution for an aluminum electrolytic capacitor comprising a.
본 발명의 다른 견지에 의하면,According to another aspect of the present invention,
당량비가 1∼2로된 하나 또는 그 이상의 화학식 HOOC-(CH2)n-COOH (n = 2∼10)의 유기 디카르복시산과 하나 또는 그 이상의 화학식 ((CH2)a(CH3))bNH3-b(a=0∼3, b=1∼3)의 아민 염기로 구성되는 전해질 10∼35중량%,One or more organic dicarboxylic acids of the equivalent ratio of 1 to 2 of the formula HOOC- (CH 2 ) n -COOH (n = 2 to 10) and one or more of the formula ((CH 2 ) a (CH 3 )) b 10 to 35% by weight of an electrolyte composed of an amine base of NH 3-b (a = 0 to 3, b = 1 to 3),
에틸렌 글리콜, 디에틸렌 글리콜 및 이들의 혼합물로 구성되는 그룹으로 부터 선택된 용매 60∼85중량% 및60 to 85% by weight of a solvent selected from the group consisting of ethylene glycol, diethylene glycol and mixtures thereof
수분 3∼7중량%,Moisture 3-7% by weight,
를 포함하여 이루어지는 알루미늄 전해 콘덴서용 전해액이 적용된 중, 고압용 알루미늄 전해 콘덴서가 제공된다.Provided is a medium and high pressure aluminum electrolytic capacitor, to which an electrolytic solution for an aluminum electrolytic capacitor, comprising: is applied.
이하, 본 발명에 대하여 상세히 설명한다.EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.
본 발명에 의하면, 탄소수 4-12 (C4-C12)의 유기 디카르복시산을 전해질의 음이온으로 그리고 1급, 2급, 3급 아민을 전해질의 양이온으로 한, 불꽃전압이 높고고온 안정성을 우수할 뿐만 아니라, 장기간에 걸친 전해 콘덴서의 고온 수명 안정화가 확보되는 중, 고압용 전해액 및 이를 이용한 전해콘덴서가 제공된다.According to the present invention, the flame voltage is high and the high temperature stability is excellent, wherein the organic dicarboxylic acid having 4 to 12 carbon atoms (C 4 -C 12 ) is used as an anion of the electrolyte, and primary, secondary and tertiary amines are the cations of the electrolyte. In addition, a high-pressure electrolyte solution and an electrolytic capacitor using the same are provided to stabilize the high temperature life of the electrolytic capacitor over a long period of time.
본 발명에서 전해질의 음이온 성분으로는 높은 불꽃전압 및 전도도를 나타내며 용해도가 우수한 하나 또는 그 이상의 하기 화학식 1의 직쇄 유기 디카르복시산이 사용된다.In the present invention, as the anion component of the electrolyte, one or more linear organic dicarboxylic acids represented by the following Chemical Formula 1 having high spark voltage and conductivity and excellent solubility are used.
[화학식 1][Formula 1]
HOOC-(CH2)n-COOH (n = 2∼10)HOOC- (CH 2 ) n -COOH (n = 2-10)
상기 유기 디카르복시산중 n 값이 커질수록 고전압에 적용가능하나, 용해도가 감소된다. 바람직하게는 n = 7∼10인 유기 디카르복시산이 사용된다. 이종 이상의 이들 유기 디카르복시산의 혼합물이 또한 사용될 수 있다.The larger the value of n in the organic dicarboxylic acid is applicable to high voltage, but the solubility is reduced. Preferably organic dicarboxylic acids with n = 7-10 are used. Mixtures of two or more of these organic dicarboxylic acids may also be used.
본 발명에서 전해질의 양이온 성분으로는 하나 또는 그 이상의 하기 화학식 2의 아민이 사용된다.In the present invention, one or more amines represented by the following Chemical Formula 2 are used as the cationic component of the electrolyte.
[화학식 2][Formula 2]
((CH2)a(CH3))bNH3-b(a=0∼3, b=1∼3)((CH 2 ) a (CH 3 )) b NH 3-b (a = 0 to 3, b = 1 to 3)
상기 화학식 2의 1급 아민류(((CH2)a(CH3))NH2(a=0∼3)), 2급 아민류(((CH2)a(CH3))2NH(a=0∼3)), 3급 아민류(((CH2)a(CH3))3N(a=0∼3))중 1종 또는 2종의 혼합 아민이 전해질의 염기부분으로 사용된다.Primary amines of the general formula ( 2 ) (((CH 2 ) a (CH 3 )) NH 2 (a = 0 to 3)), secondary amines (((CH 2 ) a (CH 3 )) 2 NH (a = 0-3)), or one or two mixed amines of tertiary amines (((CH 2 ) a (CH 3 )) 3 N (a = 0 to 3)) are used as the base portion of the electrolyte.
상기 아민의 CH2가 너무 길어지면, 즉 a=3을 초과하면 디카르복시산과 중화되기 어려움으로 a=0∼3인 아민이 사용된다. 상기 아민의 2종 이상의 혼합물이 또한 사용될 수 있다.When the CH 2 of the amine becomes too long, i.e., when a = 3, an amine having a = 0 to 3 is used due to difficulty in neutralizing with dicarboxylic acid. Mixtures of two or more of these amines may also be used.
이때, 전해액을 구성하는 산인 유기 디카르복시산과 염기인 아민은 당량비가 1∼2이 되도록 사용된다. 본 발명에서 당량비란 산의 당량/염기의 당량으로 정의된다. 전해액의 화성조건은 pH 4∼10이며, 따라서, 전해액의 pH가 상기 화성조건 범위를 충족하도록 하기 위해 당량비가 1∼2가 되도록 디카르복시산과 아민이 사용된다. 당량비가 1미만이면 pH가 너무 높아지고 아민의 증기압 증대로 인하여 휘발될 수 있다. 당량비가 2를 초과하면 화성조건에 필요한 pH보다 전해질의 pH가 낮아져 화성시 바람직하지 않을 뿐만 아니라 또한, 유기산의 석출을 초래할 수 있다.At this time, the organic dicarboxylic acid which is an acid which comprises electrolyte solution, and the amine which is a base are used so that equivalence ratio may be 1-2. In the present invention, the equivalent ratio is defined as the equivalent of acid / base equivalent. The chemical conversion conditions of the electrolyte solution are pH 4-10, and therefore, dicarboxylic acid and amine are used so that the equivalent ratio is 1 to 2 so that the pH of the electrolyte solution satisfies the chemical conversion condition range. If the equivalent ratio is less than 1, the pH may be too high and volatilized due to the increased vapor pressure of the amine. When the equivalent ratio exceeds 2, the pH of the electrolyte is lower than the pH required for chemical conversion conditions, which is undesirable when chemical conversion, and may also cause precipitation of organic acids.
본 발명의 전해액에서는 전해질의 염기성 부분으로서 측쇄가 큰 1급 내지 3급 아민류를 사용함으로써, 화합물간의 입체적 장애로 인하여 종래 전해액에서 문제시되던 에틸렌 글리콜등의 용매와 유기산의 에스테르화 반응이 지연되고, 극 고온에 적용되는 경우에도 전해질 분자내의 탈수축합반응이 방지됨으로 종래 암모늄계 전해액의 성능열화, 전극의 부식 및 제품의 ESR 증대, 내전압 강하, 쇼트 폭파등의 고장발생 원인이 제거된다.In the electrolyte solution of the present invention, by using primary to tertiary amines having a large side chain as the basic portion of the electrolyte, esterification reaction between a solvent such as ethylene glycol and an organic acid, which has been a problem in the conventional electrolyte due to steric hindrance between compounds, is delayed. Even when applied at a high temperature, the dehydration condensation reaction in the electrolyte molecules is prevented, thereby eliminating the causes of failures such as deterioration of the performance of the conventional ammonium electrolyte, corrosion of the electrode, increase of ESR of the product, drop of withstand voltage and short blasting.
당량비(산의 당량/염기의 당량)가 1∼2로된 디카르복시산과 아민의 혼합 전해질은 전해액의 총 중량을 기준으로 10∼35중량%로 사용된다. 전해질(디카르복시산과 아민)이 10중량%미만으로 사용되면 전해액의 비저항이 커지며 35중량%를 초과하면 전해질이 용해되지 않고 석출된다.The mixed electrolyte of dicarboxylic acid and amine having an equivalent ratio (equivalent to acid / base equivalent) of 1 to 2 is used at 10 to 35% by weight based on the total weight of the electrolyte. When the electrolyte (dicarboxylic acid and amine) is used at less than 10% by weight, the specific resistance of the electrolyte is increased, and when the electrolyte exceeds 35% by weight, the electrolyte does not dissolve and precipitates.
용매로는 에틸렌글리콜, 디에틸렌글리콜 및 그 혼합물이 전해액의 총 중량을 기준으로 60∼85중량%로 사용된다. 용매의 사용양이 60중량%미만이면 함유되어 있는 전해질을 비롯한 용질이 석출되고, 85중량%를 초과하면 비저항이 높아져 우수한 제품 손실 특성을 얻기 어렵다.As the solvent, ethylene glycol, diethylene glycol and mixtures thereof are used at 60 to 85% by weight based on the total weight of the electrolyte. If the amount of the solvent used is less than 60% by weight, solutes, including the electrolyte contained, are precipitated. If the amount is more than 85% by weight, the specific resistance is increased, so that excellent product loss characteristics are difficult to be obtained.
또한, 전해액의 화성능을 개선하기 위해 전해액의 총 중량을 기준으로 수분이 3∼7중량% 함유된다. 수분 함량이 3중량% 미만이면 산소공급원이 충분하지 않아 화성되지 않으며, 7중량%를 초과하면 증기압이 증대되며, 장기 신뢰성 측면에서 알루미늄이 수화반응을 일으켜 누설전류를 커지게하는 원인이 된다.In addition, in order to improve the chemical conversion performance of the electrolyte solution, 3 to 7% by weight of water is contained based on the total weight of the electrolyte solution. If the moisture content is less than 3% by weight, the oxygen source is not enough to be converted, and if it exceeds 7% by weight, the vapor pressure is increased, and in the long-term reliability, aluminum causes a hydration reaction to increase the leakage current.
나아가, 붕산, 만니톨 및 인산을 포함하는 전해액에 통상적으로 사용되는 부가적인 첨가제가 전해액의 물성을 고려하여 통상 사용되는 일반적인 사용양의 범위내에서 적정량 사용될 수 있다. 붕산은 내전압 상승을 위한 첨가제로서 치밀한 화성피막을 형성하며, 만니톨은 붕산과의 상호작용으로 붕산의 작용을 보조한다. 인산은 피막의 내수성을 증대시킨다.Furthermore, additional additives commonly used in electrolytes containing boric acid, mannitol, and phosphoric acid may be used in appropriate amounts within the range of general use amounts that are commonly used in consideration of the physical properties of the electrolyte. Boric acid forms a dense chemical film as an additive for increasing the breakdown voltage, and mannitol assists the action of boric acid by interacting with boric acid. Phosphoric acid increases the water resistance of the film.
상기 본 발명의 전해액에서는 에스테르화 반응이 지연되고, 극고온에서의 전해질 분자내의 탈수축합반응이 방지됨으로 이를 중,고압용 알루미늄 전해 콘덴서에 적용시, 고온에서 전해질의 열화가 지연되어, 전해 콘덴서의 고온에서의 장시간에 걸친 제품 안정성이 확보된다. 또한, 상기 전해질 열화에 의한 부반응물인 아미드가 생성되지 않음으로 전해콘덴서의 부식이 방지되고 제품 신뢰성이 증대된다. 나아가, 전해질의 용해도가 증대됨으로 저저항화 및 우수한 저온특성을 나타낸다. 고온에서의 비저항, 제품의 용량변화 및 ESR변화가 작으며, 150℃이상의 고온에서 1000시간에 걸친 제품 신뢰성을 나타낸다.In the electrolyte solution of the present invention, the esterification reaction is delayed, and the dehydration and condensation reaction in the electrolyte molecule at the extremely high temperature is prevented. When this is applied to a medium and high pressure aluminum electrolytic capacitor, the degradation of the electrolyte at a high temperature is delayed, Long term product stability at high temperatures is ensured. In addition, since the amide, which is a side reaction product due to the electrolyte deterioration, is not generated, corrosion of the electrolytic capacitor is prevented and product reliability is increased. Furthermore, the solubility of the electrolyte is increased, resulting in low resistance and excellent low temperature characteristics. Resistivity at high temperature, capacity change of product and change of ESR are small, and it shows product reliability over 1000 hours at high temperature over 150 ℃.
또한, 본 발명의 전해액을 이용함으로써, 알루미늄 전해 콘덴서의 소용량화에 따른 허용 리플 증대 및 사용온도의 고온화등 사용자의 요구에 부합하는 성능을 보유한 중, 고압 제품 개발 및 제품 신뢰성의 향상에 이용가능한 것이다.In addition, by using the electrolytic solution of the present invention, it can be used for development of medium and high pressure products and improvement of product reliability, which have performances that meet user demands such as increase in allowable ripple and increase in use temperature due to the small capacity of aluminum electrolytic capacitors. .
이하, 실시예를 통하여 본 발명에 대하여 상세히 설명한다.Hereinafter, the present invention will be described in detail through examples.
실시예 1Example 1
하기 표 1의 전해액 구성에 나타낸 각 성분 및 각각 기재되어 있는 함량으로 중화, 가온 용해하여 종례예 1 내지 3 및 발명예 1 내지 4의 전해액으로 제조하였다. 전해액 제조시 약 80℃로 가온하였다.Each component shown in the electrolyte solution composition of Table 1 below, and neutralized and heated to the content described, respectively, was prepared as the electrolyte solution of Examples 1-3 and Inventive Examples 1-4. When the electrolyte was prepared, it was heated to about 80 ° C.
제조직 후 각 전해액의 30℃에서의 비저항과, 150℃에서 250시간동안 고온 밀폐 방치한 후의 30℃에서의 비저항을 비저항 측정기로 측정하여 그 결과를 표 1에 나타내었다.The specific resistance at 30 ° C. of each electrolyte solution immediately after manufacture and the specific resistance at 30 ° C. after being left to stand at high temperature for 250 hours at 150 ° C. were measured with a specific resistance meter, and the results are shown in Table 1.
[표 1]TABLE 1
상기 표 1에서 알 수 있듯이, 종래예에 비하여 본 발명에 의한 전해액은 초기치 비저항과 150℃에서 250시간 경과시의 비저항의 변화가 현저하게 작았다.As can be seen from Table 1, compared with the conventional example, the electrolyte solution according to the present invention had a remarkably small change in initial resistivity and specific resistivity after 250 hours at 150 ° C.
실시예 2Example 2
상기 실시예 1의 종래예 2 및 발명예 3의 전해액을 250WV-22μF 의 전해 콘덴서에 적용하여 초기 및 리플 중첩 500시간 및 1000시간 후의 용량, 손실 및 누설전류 특성을 측정하여 하기 표 2에 나타내었다. (시험조건:150℃, DC + 리플 전류200㎃ 중첩)The electrolytic solutions of the conventional examples 2 and 3 of Example 1 were applied to an electrolytic capacitor of 250 WV-22 μF, and the capacity, loss, and leakage current characteristics after 500 hours and 1000 hours of initial and ripple overlap were measured, and are shown in Table 2 below. . (Test conditions: 150 ℃, DC + ripple current of 200mA superimposed)
[표 2]TABLE 2
상기 표 2에서 알 수 있듯이, 종례예 2의 전해액을 전해 콘덴서에 적용한 경우, 내부 가스가 급격히 증가하고 케이스 내부의 내압이 증가함에 따라 광폭기능에 의해 가스가 외부로 유출(벤트(vent) 작동)되고 고무마개가 돌출되는 불량을 나타냄에 반하여 발명예 3은 1000시간 경과시에도 우수한 용량, 손실 및 누설전류 특성을 나타내었다.As can be seen in Table 2, when the electrolytic solution of Example 2 is applied to an electrolytic capacitor, the gas flows out to the outside by the wide function as the internal gas rapidly increases and the internal pressure inside the case increases (vent operation). On the contrary, inventive example 3 showed excellent capacity, loss and leakage current characteristics even after 1000 hours.
본 발명의 전해액 및 이를 이용한 중, 고압용 알루미늄 전해 콘덴서는 고온안정성이 우수한 것으로 장시간에 걸쳐 제품 안정성이 확보된다. 또한, 전해질 열화에 의한 부반응물인 아미드가 생성되지 않음으로 전해콘덴서의 부식이 방지되고 제품신뢰성이 증대된다.The electrolytic solution of the present invention and the medium and high pressure aluminum electrolytic capacitor using the same have excellent high temperature stability, thereby ensuring product stability over a long period of time. In addition, since no side reaction product amide is generated due to electrolyte degradation, corrosion of the electrolytic capacitor is prevented and product reliability is increased.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01293609A (en) * | 1988-05-23 | 1989-11-27 | Matsushita Electric Ind Co Ltd | Electrolytic solution for driving electrolytic capacitor |
| US5111365A (en) * | 1991-06-20 | 1992-05-05 | U.S. Philips Corporation | Electrolytic capacitor provided with a low resistivity electrolyte |
| JPH04320316A (en) * | 1991-04-19 | 1992-11-11 | Elna Co Ltd | Electrolyte for driving electrolytic capacitor and electrolytic capacitor |
| US5175674A (en) * | 1992-03-24 | 1992-12-29 | North American Philips Corporation | Electrolyte containing a novel depolarizer and an electrolytic capacitor containing said electrolyte |
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2002
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01293609A (en) * | 1988-05-23 | 1989-11-27 | Matsushita Electric Ind Co Ltd | Electrolytic solution for driving electrolytic capacitor |
| JPH04320316A (en) * | 1991-04-19 | 1992-11-11 | Elna Co Ltd | Electrolyte for driving electrolytic capacitor and electrolytic capacitor |
| US5111365A (en) * | 1991-06-20 | 1992-05-05 | U.S. Philips Corporation | Electrolytic capacitor provided with a low resistivity electrolyte |
| US5175674A (en) * | 1992-03-24 | 1992-12-29 | North American Philips Corporation | Electrolyte containing a novel depolarizer and an electrolytic capacitor containing said electrolyte |
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