JP3242430B2 - Electrolytic capacitor - Google Patents
Electrolytic capacitorInfo
- Publication number
- JP3242430B2 JP3242430B2 JP32707691A JP32707691A JP3242430B2 JP 3242430 B2 JP3242430 B2 JP 3242430B2 JP 32707691 A JP32707691 A JP 32707691A JP 32707691 A JP32707691 A JP 32707691A JP 3242430 B2 JP3242430 B2 JP 3242430B2
- Authority
- JP
- Japan
- Prior art keywords
- electrolytic
- solution
- electrolytic capacitor
- paper
- electrolytic solution
- 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.)
- Expired - Fee Related
Links
Landscapes
- Electric Double-Layer Capacitors Or The Like (AREA)
- Paper (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、電解コンデンサに関す
るものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrolytic capacitor.
【０００２】[0002]
【従来の技術】従来より低圧用電解コンデンサの電解液
としては、エチレングリコ−ルを主溶媒として、アジピ
ン酸塩を溶解した電解液が多用されていたが、近年、電
解コンデンサの低インピ−ダンス化、高信頼化への対応
に伴い、γ−ブチロラクトンを主溶媒として、フタル酸
のテトラアルキルアンモニウム塩を溶解した電解液が一
般的に使用されている。2. Description of the Related Art Conventionally, as an electrolytic solution of an electrolytic capacitor for low pressure, an electrolytic solution in which adipate is dissolved using ethylene glycol as a main solvent has been frequently used. In response to the demand for higher reliability and higher reliability, an electrolytic solution containing γ-butyrolactone as a main solvent and a tetraalkylammonium salt of phthalic acid dissolved therein is generally used.
【０００３】[0003]
【発明が解決しようとする課題】電解コンデンサの電解
液として、γ−ブチロラクトンへフタル酸のテトラアル
キルアンモニウム塩を溶解したものは、溶質のエステル
化、変質などが起こりにくいため、高温雰囲気中におけ
る信頼性が非常に高い。しかし、この電解液の主溶媒に
使用しているγ−ブチロラクトンは、高温雰囲気中にお
ける封口部からの蒸散がエチレングリコ−ルなどに比べ
て激しいため、特に小サイズの電解コンデンサでは、封
口部に気密性の良いブチルゴムを用いても、電解コンデ
ンサが保持する電解液量は時間と共に大きく減少し、そ
れに伴い容量減少、ｔａｎδ増加が発生し、さらにはこ
の電解液量の減少が電解コンデンサの寿命を規定してし
まう。As an electrolytic solution for an electrolytic capacitor, a solution obtained by dissolving a tetraalkylammonium salt of phthalic acid in γ-butyrolactone is unlikely to cause esterification or alteration of the solute. Very high. However, since γ-butyrolactone used as the main solvent of this electrolytic solution evaporates from the sealing portion in a high-temperature atmosphere more intensely than ethylene glycol or the like, especially in a small-sized electrolytic capacitor, Even if butyl rubber with good airtightness is used, the amount of electrolytic solution held by the electrolytic capacitor greatly decreases with time, and the capacity and tan δ increase accordingly, and further, the decrease in the amount of electrolytic solution extends the life of the electrolytic capacitor. I will specify it.
【０００４】[0004]
【課題を解決するための手段】本発明は上述の問題点を
解決するもので、高温雰囲気中における電解液の蒸発量
を大幅に低下し、電解コンデンサの寿命特性を大幅に向
上させるものである。すなわち、陽極箔と陰極箔との間
に電解紙を介在させて巻回したコンデンサ素子に電解液
を含浸させた電解コンデンサにおいて、上記電解液が、
γ−ブチロラクトンを主溶媒として、有機酸のテトラア
ルキルアンモニウム塩あるいはテトラアルキルホスホニ
ウム塩を溶解した溶液中に、ＳｉＯ ２ を溶解させ、かつ
予め上記電解紙中にゲル化剤としてのリン化合物，ホウ
素化合物あるいは有機酸のアンモニウム塩が含有されて
いることを特徴とする電解コンデンサである。なお、電
解紙中にリン化合物などゲル化剤を含有させる方法は、
電解紙を抄紙する際の液中にゲル化剤を溶解しておく方
法、電解紙を抄紙した後ゲル化剤の溶解した液中に浸漬
させる方法など、いかなる方法を用いてもよい。SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and it is intended to drastically reduce the evaporation amount of an electrolytic solution in a high-temperature atmosphere and to greatly improve the life characteristics of an electrolytic capacitor. . That is, in an electrolytic capacitor in which the electrolytic solution is impregnated in a capacitor element wound with an electrolytic paper interposed between the anode foil and the cathode foil, the electrolytic solution is
SiO 2 is dissolved in a solution of a tetraalkylammonium salt or a tetraalkylphosphonium salt of an organic acid with γ-butyrolactone as a main solvent, and a phosphorus compound or a boron compound as a gelling agent is previously dissolved in the electrolytic paper. Alternatively, the electrolytic capacitor includes an ammonium salt of an organic acid. In addition, the method of including a gelling agent such as a phosphorus compound in the electrolytic paper,
Any method may be used, such as a method in which a gelling agent is dissolved in a liquid used for making an electrolytic paper, a method in which an electrolytic paper is made and then dipped in a solution in which the gelling agent is dissolved.
【０００５】[0005]
【作用】本発明の電解液中へ配合されたＳｉＯ ２ は、通
常は１０ｍμ程度の粒子であり、粒子表面はＳｉＯＨ基
およびＯＨ−１イオンが存在して負に帯電しており、こ
れが周囲の陽イオンと電気二重層を形成し、相互の反発
により安定化している。しかし、この電気二重層は電解
液中に価数の大きなイオンが存在する場合、あるいは、
電解液ｐＨがアルカリ領域になった場合には破壊されて
しまい、ＳｉＯ ２ 粒子同士が網目状に接合することによ
って、電解液のゲル化が生じる。よって、本発明に係わ
る電解液を用いた電解コンデンサは、コンデンサ素子へ
の常温での電解液の含浸の際、電解紙中に含有されてい
るリン化合物，ホウ素化合物あるいは有機酸のアンモニ
ウム塩などにより、電解液中のＳｉＯ ２ 粒子表面の電気
二重層が破壊されることにより、電解液のゲル化が瞬時
に起こるため、従来の電解液に比べて高温雰囲気中での
電解液の蒸散量が低下し、電解コンデンサの寿命特性を
大幅に向上させることが可能となる。なお、この電解液
のゲル化は、有機酸のカチオンがテトラメチルアンモニ
ウムの場合が最も顕著である。The SiO 2 compounded in the electrolyte of the present invention is usually about 10 μm particles, and the surface of the particles is negatively charged due to the presence of SiOH groups and OH- 1 ions. It forms an electric double layer with cations and is stabilized by mutual repulsion. However, this electric double layer can be used when high valence ions exist in the electrolyte, or
If the pH of the electrolytic solution is in an alkaline region, the electrolyte solution is destroyed, and the SiO 2 particles are joined to each other in a network, thereby causing the electrolytic solution to gel. Therefore, the electrolytic capacitor using the electrolytic solution according to the present invention is characterized in that when the capacitor element is impregnated with the electrolytic solution at normal temperature, the electrolytic compound contains a phosphorus compound, a boron compound or an ammonium salt of an organic acid, etc. Since the electric double layer on the surface of the SiO 2 particles in the electrolytic solution is destroyed, the electrolytic solution gels instantaneously, so that the amount of the electrolytic solution evaporated in a high-temperature atmosphere is reduced as compared with the conventional electrolytic solution. However, the life characteristics of the electrolytic capacitor can be significantly improved. The gelation of the electrolytic solution is most remarkable when the cation of the organic acid is tetramethylammonium.
【０００６】[0006]
【実施例】以下、本発明の実施例について説明する。表
１は、溶質量１５ｗｔ％の際の本発明の電解液と従来の
電解液の組成、比抵抗および火花発生電圧についての比
較例を示す。なお、表１中電解液試料記号Ａは従来例、
Ｂ，Ｃ，Ｄ，Ｅは本発明例であり、また、表１中ＧＢＬ
はγ−ブチロラクトンを示す。Embodiments of the present invention will be described below. Table 1 shows a comparative example of the composition, specific resistance, and spark generation voltage of the electrolytic solution of the present invention and the conventional electrolytic solution when the dissolved mass is 15 wt%. The electrolyte sample symbol A in Table 1 is a conventional example,
B, C, D, and E are examples of the present invention.
Represents γ-butyrolactone.
【０００７】[0007]
【表１】 [Table 1]
【０００８】表１から明らかなように、本発明に係る試
料記号Ｂ，Ｃ，Ｄ，Ｅの電解液は従来の電解液に比べ、
耐電圧が大幅に向上している。表２は、電解紙として、 ａ：マニラ麻による従来の電解紙 ｂ：ａ．に０．０１ｍｇ／ｃｍ２の次亜リン酸アンモニ
ウムを含有された電解紙 ｃ：ａ．に１ｍｇ／ｃｍ２の次亜リン酸アンモニウムを
含有された電解紙 ｄ：ａ．に１ｍｇ／ｃｍ２ほう酸を含有させた電解紙 ｅ：ａ．に１ｍｇ／ｃｍ２フタル酸アンモニウムを含有
させた電解紙 をそれぞれ巻回した５種類のコンデンサを形成し、表１
中電解液試料記号Ａの従来の電解液と、本発明例として
試料記号Ｃを示す電解液をそれぞれ含浸して、定格２５
Ｖ ３３０μＦの電解コンデンサを試作し、１０５℃
２０００時間高温負荷試験を行った最の、電解コンデン
サの容量変化率および重量変化量を示す。As is clear from Table 1, the electrolytes of the sample symbols B, C, D, and E according to the present invention are different from the conventional electrolytes.
The withstand voltage has been greatly improved. Table 2 shows that, as the electrolytic paper, a: conventional electrolytic paper by Manila hemp b: a. Electrolytic paper containing 0.01 mg / cm 2 of ammonium hypophosphite c: a. Electrolytic paper containing 1 mg / cm 2 of ammonium hypophosphite d: a. Containing 1 mg / cm 2 boric acid in e: a. Five types of capacitors were formed by winding electrolytic paper containing 1 mg / cm 2 ammonium phthalate on each of the sheets.
The conventional electrolyte solution of the sample symbol A of the medium electrolyte and the electrolyte solution of the sample symbol C as an example of the present invention were each impregnated with the electrolyte solution.
Prototype electrolytic capacitor of V330μF, 105 ℃
The capacity change rate and the weight change amount of the electrolytic capacitor at the end of the 2000-hour high-temperature load test are shown.
【０００９】[0009]
【表２】 [Table 2]
【００１０】表２から明らかなように、本発明に係る電
解液および電解紙を用いた電解コンデンサは、長時間の
高温雰囲気中における試験においても全ての特性に問題
がなく、かつ、電解液の蒸散による電解コンデンサ重量
の減少が少ない。また、電解液中ＳｉＯ ２ は高温雰囲気
中に長時間放置することによっても、電解液の増粘・ゲ
ル化が発生するため、通常の電解紙を用いても特性が向
上する。なお、ＳｉＯ ２ の配合量は、混合溶媒１００ｇ
に対し０．１ｇ未満、あるいは、ゲル化剤としてのリン
化合物，ホウ素化合物あるいは有機酸のアンモニウム塩
含有量が、電解紙１ｃｍ ２ 当たり０．０１ｍｇ未満の場
合では電解液の常温でのゲル化が起こらず、また、１５
ｇを超えた場合は析出がみられる。As is clear from Table 2, the electrolytic capacitor using the electrolytic solution and the electrolytic paper according to the present invention has no problem in all the characteristics even in a test in a high-temperature atmosphere for a long time. Less loss of electrolytic capacitor weight due to transpiration. Further, the electrolyte solution SiO 2 by allowing it to stand a long time in a high temperature atmosphere, because the thickening gelling of the electrolyte occurs, the characteristics are improved even with a conventional electrolytic paper. The amount of SiO 2 was 100 g of the mixed solvent.
If the content of the ammonium salt of a phosphorus compound, a boron compound or an organic acid as a gelling agent is less than 0.01 mg per 1 cm 2 of the electrolytic paper, the gelation of the electrolytic solution at room temperature may occur. Not happening, and 15
If it exceeds g, precipitation is observed.
【００１１】[0011]
【発明の効果】以上のように、γ−ブチロラクトンを主
溶媒として、有機酸のテトラアルキルアンモニウム塩あ
るいはテトラアルキルホスホニウム塩を溶解した溶液中
に、ＳｉＯ ２ を溶解したことを特徴とする電解液を、予
め電解紙中にゲル化剤としてのリン化合物，ホウ素化合
物あるいは有機酸のアンモニウム塩が含有されているコ
ンデンサ素子に含浸することによって、電解液を常温に
おいてゲル化させることを特徴とする電解コンデンサ
は、高温雰囲気中においても高い信頼性を有し、工業的
ならびに実用的価値の大なるものである。As described above, an electrolytic solution characterized by dissolving SiO 2 in a solution in which a tetraalkylammonium salt or a tetraalkylphosphonium salt of an organic acid is dissolved using γ-butyrolactone as a main solvent. An electrolytic capacitor characterized in that an electrolytic solution is gelled at room temperature by previously impregnating a capacitor element containing a phosphorus compound, a boron compound or an ammonium salt of an organic acid as a gelling agent in electrolytic paper. Has high reliability even in a high-temperature atmosphere and is of great industrial and practical value.
Claims (4)
せて巻回したコンデンサ素子に電解液を含浸させた電解
コンデンサにおいて、上記電解液が、γ−ブチロラクト
ンを主溶媒として、有機酸のテトラアルキルアンモニウ
ム塩あるいはテトラアルキルホスホニウム塩を溶解した
溶液中に、ＳｉＯ ２ を溶解させ、かつ予め上記電解紙中
にゲル化剤としてのリン化合物，ホウ素化合物あるいは
有機酸のアンモニウム塩が含有されていることを特徴と
する電解コンデンサ。1. An electrolytic capacitor in which an electrolytic solution is impregnated in a capacitor element wound with electrolytic paper interposed between an anode foil and a cathode foil, wherein the electrolytic solution comprises γ-butyrolactone as a main solvent and an organic solvent. SiO 2 is dissolved in a solution in which a tetraalkylammonium salt or tetraalkylphosphonium salt of an acid is dissolved, and a phosphorous compound, a boron compound or an ammonium salt of an organic acid as a gelling agent is previously contained in the electrolytic paper. An electrolytic capacitor, characterized in that:
００ｇに対し０．１〜１５ｇ存在することを特徴とする
請求項１の電解コンデンサ。2. The SiO 2 in the electrolyte is mixed with a mixed solvent 1
2. The electrolytic capacitor according to claim 1, wherein the amount is 0.1 to 15 g per 100 g.
合物，ホウ素化合物あるいは有機酸のアンモニウム塩含
有量は、電解紙１ｃｍ ２ 当たり０．０１ｍｇ以上存在す
ることを特徴とする請求項１の電解コンデンサ。3. The electrolytic paper according to claim 1, wherein the content of the ammonium salt of a phosphorus compound, a boron compound or an organic acid as a gelling agent in the electrolytic paper is 0.01 mg or more per 1 cm 2 of the electrolytic paper. Electrolytic capacitor.
含浸することによって、電解液が常温においてゲル化す
ることを特徴とする請求項１の電解コンデンサ。4. The electrolytic capacitor according to claim 1, wherein the electrolytic solution is gelled at room temperature by impregnating the electrolytic capacitor element with the electrolytic solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32707691A JP3242430B2 (en) | 1991-11-14 | 1991-11-14 | Electrolytic capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32707691A JP3242430B2 (en) | 1991-11-14 | 1991-11-14 | Electrolytic capacitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05136003A JPH05136003A (en) | 1993-06-01 |
| JP3242430B2 true JP3242430B2 (en) | 2001-12-25 |
Family
ID=18195024
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32707691A Expired - Fee Related JP3242430B2 (en) | 1991-11-14 | 1991-11-14 | Electrolytic capacitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3242430B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100908571B1 (en) * | 2005-11-15 | 2009-07-22 | 주식회사 엘지화학 | Lithium secondary battery with excellent safety and low temperature output characteristics |
-
1991
- 1991-11-14 JP JP32707691A patent/JP3242430B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05136003A (en) | 1993-06-01 |
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