JPH02198126A - Electrolytic capacitor - Google Patents
Electrolytic capacitorInfo
- Publication number
- JPH02198126A JPH02198126A JP1848389A JP1848389A JPH02198126A JP H02198126 A JPH02198126 A JP H02198126A JP 1848389 A JP1848389 A JP 1848389A JP 1848389 A JP1848389 A JP 1848389A JP H02198126 A JPH02198126 A JP H02198126A
- Authority
- JP
- Japan
- Prior art keywords
- quaternary ammonium
- hypophosphorous acid
- ammonium salt
- organic solvent
- polar organic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003990 capacitor Substances 0.000 title claims abstract description 26
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 16
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 11
- 239000003495 polar organic solvent Substances 0.000 claims abstract description 10
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000003792 electrolyte Substances 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- -1 amine salts Chemical class 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- WSGYTJNNHPZFKR-UHFFFAOYSA-N 3-hydroxypropanenitrile Chemical compound OCCC#N WSGYTJNNHPZFKR-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- GSCLMSFRWBPUSK-UHFFFAOYSA-N beta-Butyrolactone Chemical compound CC1CC(=O)O1 GSCLMSFRWBPUSK-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- BRPNQNJKQPYBFD-UHFFFAOYSA-N hydroxyphosphinite;tetrabutylazanium Chemical compound OP[O-].CCCC[N+](CCCC)(CCCC)CCCC BRPNQNJKQPYBFD-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 description 1
- 230000001755 vocal effect Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Secondary Cells (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、電解コンデンサ、詳しくは新規な駆動用電解
液を使用した電解コンデンサに関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an electrolytic capacitor, and more particularly to an electrolytic capacitor using a novel driving electrolyte.
［従来の技術］
アルミニウムなどの弁作用金属の箔をセパレータととも
に巻回してコンデンサ素子とした電解コンデンは、一般
にコンデンサ素子に駆動用電解液を含浸し、アルミニウ
ムなどの金属ケースや合成樹脂製のケースにコンデンサ
素子を収納し、密閉した構造を有する。[Prior art] Electrolytic capacitors are made by winding a foil of a valve metal such as aluminum together with a separator to form a capacitor element.Generally, the capacitor element is impregnated with a driving electrolyte, and then the capacitor element is impregnated with a driving electrolyte, and the capacitor element is made of a metal case such as aluminum or a case made of synthetic resin. The capacitor element is housed inside and has a sealed structure.
このような電解コンデンサの駆動用電解液としては従来
、エチレングリコールなどの極性有機溶媒を主溶媒とし
、これに飽和有機酸のアンモニウム塩のように金属から
なる電極を侵食しない塩を溶解した電解液が一般に使用
されている（特公昭５８−１３０１９号公報）。Conventionally, the driving electrolyte for such electrolytic capacitors is an electrolytic solution in which the main solvent is a polar organic solvent such as ethylene glycol, and a salt that does not corrode metal electrodes, such as an ammonium salt of a saturated organic acid, is dissolved in this. is generally used (Japanese Patent Publication No. 58-13019).
［発明が解決しようとする課題］
しかしながら、前記の電解液においては、電気抵抗値の
指標である損失（ｔａｎδ）を下げるために１〜３０重
量％の水を含有させることが行われているが、この場合
には陰極箔の侵食や解離したアンモニア（ＮＨｓ）の蒸
散のため高温度におけるコンデンサの特性劣化、特に損
失（ｔａｎδ）の変化が大きいという問題点があった。[Problems to be Solved by the Invention] However, in the above-mentioned electrolytic solution, 1 to 30% by weight of water is contained in order to reduce loss (tan δ), which is an index of electrical resistance. In this case, there was a problem in that the characteristics of the capacitor deteriorated at high temperatures due to corrosion of the cathode foil and evaporation of dissociated ammonia (NHs), and in particular, the change in loss (tan δ) was large.
また、電導度が高く （電気抵抗が低く）、かつ高温で
安定な液として飽和鎖状ジカルボン酸の第４アンモニウ
ム塩を極性有機溶媒に溶解した電解液の使用が特開昭５
９−７８５２２号公報に開示されている。In addition, the use of an electrolytic solution in which a quaternary ammonium salt of a saturated chain dicarboxylic acid is dissolved in a polar organic solvent has been proposed as a liquid with high conductivity (low electrical resistance) and stability at high temperatures.
It is disclosed in Japanese Patent No. 9-78522.
しかしながら、実施例によれば、この電解液の電導度は
せいぜい９．４１１３７０ｍで、現在要求されている水
準（１２〜２５ ａｓ／ｃａｌから見れば不十分である
という問題点があった。However, according to the example, the conductivity of this electrolytic solution was at most 9.411370 m, which was insufficient compared to the currently required level (12 to 25 as/cal).
本発明は、前記の問題点を解決して、電気抵抗が低く
（電導度が高＜）、かつ高温安定性の優れた電解コンデ
ンサを提供することを目的とする。The present invention solves the above problems and provides low electrical resistance.
The purpose of the present invention is to provide an electrolytic capacitor with high conductivity (<high conductivity) and excellent high temperature stability.
［課題を解決するための手段］
本発明は、前記問題点を解決するため、極性有機溶媒に
次亜リン酸の第４アンモニウム塩を溶解してなる駆動用
電解液を使用したことを特徴とする電解コンデンサを提
供するものである。[Means for Solving the Problems] In order to solve the above-mentioned problems, the present invention is characterized by using a driving electrolyte formed by dissolving a quaternary ammonium salt of hypophosphorous acid in a polar organic solvent. The present invention provides an electrolytic capacitor that
本発明において用いられる次亜リン酸の第４アンモニウ
ム塩としては、一般式Ｒ，Ｎ”で示される第４アンモニ
ウムのアルキル基（Ｒ）の炭素数１〜１０個のもの、特
に１〜４個のものが好適に使用され、例えば次亜リン酸
テトラメチルアンモニウム、次亜リン酸テトラエチルア
ンモニウム、次亜リン酸テトラプロピルアンモニウム、
次亜リン酸テトラブチルアンモニウムなどが挙げられる
。The quaternary ammonium salt of hypophosphorous acid used in the present invention is a quaternary ammonium salt represented by the general formula R,N'' with an alkyl group (R) having 1 to 10 carbon atoms, especially one having 1 to 4 carbon atoms. For example, tetramethylammonium hypophosphite, tetraethylammonium hypophosphite, tetrapropylammonium hypophosphite,
Examples include tetrabutylammonium hypophosphite.
本発明において、次亜リン酸の第４アンモニウム塩を使
用するのは１次亜リン酸の他のアミン塩などの場合には
、電解液の電導度が低く製品のｔａｎδが大きくなって
しまい、好ましくないためである。In the present invention, the quaternary ammonium salt of hypophosphorous acid is used instead of other amine salts of primary hypophosphorous acid, because the electrolyte has a low conductivity and the tan δ of the product becomes large. This is because it is not desirable.
本発明で用いられる次亜リン酸の第４アンモニウム塩の
電解液組成中における含有量（濃度）は適宜選ぶことが
できるが、飽和溶液の状態のときに比抵抗が最も小さい
点を考慮すると１〜５０重量％が適当であり、なかでも
良好な高温安定性を得るためには５〜４０重量％が好適
である。The content (concentration) of the quaternary ammonium salt of hypophosphorous acid used in the present invention in the electrolyte composition can be selected as appropriate, but considering that the specific resistance is the lowest when it is in a saturated solution state, -50% by weight is suitable, and in order to obtain good high temperature stability, 5-40% by weight is particularly suitable.
本発明で用いる極性有機溶媒としては、電解コンデンサ
に通常使用される極性有機溶媒であればいずれも使用が
可能である。これらの溶媒の中で、アミド類、ラクトン
類、グリコール類、ニトリル類、硫黄化合物類または炭
酸塩類が好適に使用できる。好ましい溶媒の具体的な例
としては、ジメチルホルムアミド、Ｎ−メチルホルムア
ミド、γ−ブチロラクトン、β−ブチロラクトン、γ−
バレロラクトン、３−アルキル−１，３オキサゾリジン
−２−オン、Ｎ−メチルピロリドン、エチレングリコー
ル、エチレングリコール・モノアルキルエーテル、エチ
レングリコール・ジアルキルエーテル、アセトニトリル
、メチレンゲルタロニトリル、ジメチルスルホキシド、
炭酸プロピレン、エチレンシアノヒドリンなどが挙げら
れ、これらの溶媒は単独で、あるいは適宜混合して使用
される。As the polar organic solvent used in the present invention, any polar organic solvent commonly used in electrolytic capacitors can be used. Among these solvents, amides, lactones, glycols, nitriles, sulfur compounds, or carbonates can be preferably used. Specific examples of preferred solvents include dimethylformamide, N-methylformamide, γ-butyrolactone, β-butyrolactone, γ-
Valerolactone, 3-alkyl-1,3oxazolidin-2-one, N-methylpyrrolidone, ethylene glycol, ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, acetonitrile, methylene geltalonitrile, dimethyl sulfoxide,
Examples include propylene carbonate and ethylene cyanohydrin, and these solvents may be used alone or in appropriate mixtures.
本発明において、次亜リン酸の第４アンモニウム塩を含
有する駆動用電解液を得るには、この第４アンモニウム
塩を極性有機溶媒に添加してもよいが、溶媒中で次亜リ
ン酸に第４アンモニウム塩を生成可能な物質を反応させ
ることによって、この第４アンモニウム塩を生成させて
もよい。In the present invention, in order to obtain a driving electrolyte containing a quaternary ammonium salt of hypophosphorous acid, the quaternary ammonium salt may be added to a polar organic solvent. The quaternary ammonium salt may be produced by reacting a substance capable of producing the quaternary ammonium salt.
本発明では電解液中に水を含有させることは必ずしも必
要ではないが、比抵抗を下げるためには水の含有は効果
的である。ただし、ある限度以上に水の含有量を多くす
ると、内部発生ガスによる電解コンデンサのケースの膨
れや電極箔の声食を増大させる要因になるので高温度で
長時間使用する目的のためには、水の含有量はなるべく
少ない方が好ましい、したがって、コンデンサの使用目
的に対応して、水の含有量は電解液組成中０．１〜２０
重量％の範囲が好ましく、０．５〜１５重量％がさらに
好ましい。In the present invention, it is not necessary to include water in the electrolytic solution, but it is effective to lower the specific resistance. However, if the water content is increased beyond a certain limit, it will increase the swelling of the electrolytic capacitor case due to internally generated gas and the vocal corrosion of the electrode foil. It is preferable that the water content be as low as possible. Therefore, depending on the intended use of the capacitor, the water content should be between 0.1 and 20% in the electrolyte composition.
A range of % by weight is preferred, and a range of 0.5 to 15% by weight is more preferred.
本発明の電解コンデンサには、種々の態様のコンデンサ
が包含される。典型的態様としては、紙などの適宜のセ
パレータで分離したアルミニウム箔陽極とアルミニウム
箔陰極とを使用し、これらを円筒状に巻いたものをコン
デンサ素子とし、この素子に駆動用電解液を含浸させる
。電解液の含浸量としてはセパレータに対して、好まし
くは５０〜３００重量％とされる。電解液が含浸された
素子は、耐食性を有する金属や合成樹脂などのケースに
収納し、密封した構造にされる。The electrolytic capacitor of the present invention includes various types of capacitors. In a typical embodiment, an aluminum foil anode and an aluminum foil cathode separated by a suitable separator such as paper are used, these are wound into a cylindrical shape to form a capacitor element, and this element is impregnated with a driving electrolyte. . The amount of electrolytic solution impregnated is preferably 50 to 300% by weight based on the separator. The element impregnated with the electrolyte is housed in a case made of corrosion-resistant metal, synthetic resin, or the like, and has a sealed structure.
［実施例］
以下、本発明を実施例および比較例に基づいて具体的に
説明する。[Examples] The present invention will be specifically described below based on Examples and Comparative Examples.
水酸化テトラアルキルアンモニウム（アルキル基の炭素
数１〜３）の１０％水溶液と次亜リン酸とを等モル数に
なるように混合して次亜リン酸を溶解させた後、エバポ
レータにより水を除去して次亜リン酸の第４アンモニウ
ム塩を生成させ、これらを溶質として所定量を極性有機
溶媒に溶解させて実施例１〜３の電解液とした。After mixing a 10% aqueous solution of tetraalkylammonium hydroxide (alkyl group has 1 to 3 carbon atoms) and hypophosphorous acid to an equimolar number to dissolve the hypophosphorous acid, water is removed using an evaporator. This was removed to produce a quaternary ammonium salt of hypophosphorous acid, which was used as a solute and a predetermined amount was dissolved in a polar organic solvent to obtain the electrolytes of Examples 1 to 3.
これらの電解液を使用してアルミニウムを電極とする電
解コンデンサ（定格１０Ｖ、１０００μＦ）を製作し、
高温負荷試験（定格電圧印加、１０５℃、１０００時間
）を行って、１００ ｋＨｚ時のインピーダンスの変化
を測定し、その結果を第１表に示した。Using these electrolytes, we manufactured an electrolytic capacitor (rated 10V, 1000μF) with aluminum electrodes,
A high temperature load test (rated voltage applied, 105° C., 1000 hours) was conducted to measure the change in impedance at 100 kHz, and the results are shown in Table 1.
［発明の効果］
以上説明したように本発明によれば、高温条件下でのイ
ンピーダンスの変化が小さい高温安定性の優れた電解コ
ンデンサが得られる。[Effects of the Invention] As explained above, according to the present invention, an electrolytic capacitor with excellent high-temperature stability and small change in impedance under high-temperature conditions can be obtained.
Claims (3)
を溶解してなる駆動用電解液を使用したことを特徴とす
る電解コンデンサ。(1) An electrolytic capacitor characterized by using a driving electrolytic solution formed by dissolving a quaternary ammonium salt of hypophosphorous acid in a polar organic solvent.
の含有量が１〜５０重量％である特許請求の範囲第１項
記載の電解コンデンサ。(2) The electrolytic capacitor according to claim 1, wherein the content of the quaternary ammonium salt of hypophosphorous acid in the electrolytic solution is 1 to 50% by weight.
のアルキル基（Ｒ）の炭素数が１〜１０個である特許請
求の範囲第１項または第２項記載の電解コンデンサ。(3) The electrolytic capacitor according to claim 1 or 2, wherein the alkyl group (R) of the quaternary ammonium represented by the general formula R_4N^+ has 1 to 10 carbon atoms.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1848389A JPH02198126A (en) | 1989-01-27 | 1989-01-27 | Electrolytic capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1848389A JPH02198126A (en) | 1989-01-27 | 1989-01-27 | Electrolytic capacitor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02198126A true JPH02198126A (en) | 1990-08-06 |
Family
ID=11972883
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1848389A Pending JPH02198126A (en) | 1989-01-27 | 1989-01-27 | Electrolytic capacitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02198126A (en) |
-
1989
- 1989-01-27 JP JP1848389A patent/JPH02198126A/en active Pending
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