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JP3487911B2 - Electrolyte for driving electrolytic capacitors - Google Patents

Electrolyte for driving electrolytic capacitors

Info

Publication number
JP3487911B2
JP3487911B2 JP17231494A JP17231494A JP3487911B2 JP 3487911 B2 JP3487911 B2 JP 3487911B2 JP 17231494 A JP17231494 A JP 17231494A JP 17231494 A JP17231494 A JP 17231494A JP 3487911 B2 JP3487911 B2 JP 3487911B2
Authority
JP
Japan
Prior art keywords
weight
electrolytic solution
high temperature
electrolytic capacitor
acid
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
Application number
JP17231494A
Other languages
Japanese (ja)
Other versions
JPH0837132A (en
Inventor
泉 藤馬
Original Assignee
ニチコン株式会社
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by ニチコン株式会社 filed Critical ニチコン株式会社
Priority to JP17231494A priority Critical patent/JP3487911B2/en
Publication of JPH0837132A publication Critical patent/JPH0837132A/en
Application granted granted Critical
Publication of JP3487911B2 publication Critical patent/JP3487911B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54Electrolytes
    • H01G11/58Liquid electrolytes
    • H01G11/62Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein

Landscapes

  • 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)

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は、電解コンデンサの駆動
用電解液の改良に関し、高温での寿命特性の長期安定化
を実現した電解コンデンサの駆動用電解液(以下、単に
電解液という)に関するものである。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improved electrolyte for driving an electrolytic capacitor, and more particularly to an electrolyte for driving an electrolytic capacitor (hereinafter, simply referred to as "electrolyte") which has long-term stability of life characteristics at high temperature. It is a thing.

【0002】[0002]

【従来の技術】電解液は、電解コンデンサにおける陽極
と陰極との間にあって、導電媒体として働くものであ
り、電解液の特性が電解コンデンサ特性を左右する大き
な要因となる。その中でも広温度範囲に用いる電解コン
デンサの電解液は、下記の性質が優れたものでなければ
ならない。 (1)沸点が高く、高温において蒸気圧が低い。 (2)低温でも粘度が上がらず、導電度が高い。 (3)凝固点が低い。 (4)火花電圧が可能な限り高い。 (5)陽極酸化皮膜の形成能が良い。 (6)誘電体を初めとする電解コンデンサ部分を侵すこ
となく、特に腐食を発生しない。 (7)高温下で長時間放置しても、その特性において安
定している。
2. Description of the Related Art An electrolytic solution is present between an anode and a cathode in an electrolytic capacitor and serves as a conductive medium, and the characteristics of the electrolytic solution are a major factor that influences the characteristics of the electrolytic capacitor. Among them, the electrolytic solution of the electrolytic capacitor used in a wide temperature range must have the following excellent properties. (1) High boiling point and low vapor pressure at high temperature. (2) Viscosity does not increase even at low temperature, and conductivity is high. (3) The freezing point is low. (4) The spark voltage is as high as possible. (5) Good ability to form an anodized film. (6) Corrosion does not particularly occur without damaging the electrolytic capacitor portion including the dielectric. (7) The characteristics are stable even when left at high temperature for a long time.

【0003】従来の電解コンデンサの低圧用電解液とし
ては、エチレングリコールと水を混合した溶媒に、安息
香酸アンモニウムおよびアジピン酸アンモニウムを添加
したものが用いられていた。
As a low-voltage electrolytic solution for a conventional electrolytic capacitor, a solvent prepared by adding ammonium benzoate and ammonium adipate to a solvent prepared by mixing ethylene glycol and water has been used.

【0004】[0004]

【発明が解決しようとする課題】この電解液は、上記の
(1)〜(6)項は一応満足するものであるが、(7)
項の高温下での特性の安定性に関して問題があった。す
なわち、水の沸点が100℃と低いため、高温での使用
に際して溶媒が揮散しやすい上、溶質として使用した有
機酸アンモニウムが高温下で分解し、アンモニアガスと
して散逸することによって、電解液の比抵抗が増大し、
電解コンデンサの損失角の正接(tanδ)が増加する
のである。
This electrolytic solution satisfies the above items (1) to (6), but (7)
There was a problem with respect to the stability of the characteristics under high temperature. That is, since the boiling point of water is as low as 100 ° C., the solvent is easily volatilized at the time of use at high temperature, and the organic acid ammonium used as a solute is decomposed at high temperature and dissipated as ammonia gas, resulting in a ratio of the electrolyte solution. Increased resistance,
The tangent (tan δ) of the loss angle of the electrolytic capacitor increases.

【0005】本発明は、上記問題点を解決するもので、
高温下における電解コンデンサの静電容量変化及びta
nδ変化を改善することができる電解コンデンサの駆動
用電解液を提供することを目的とするものである。
The present invention solves the above problems,
Capacitance change and ta of electrolytic capacitor under high temperature
An object of the present invention is to provide an electrolytic solution for driving an electrolytic capacitor, which can improve the change in nδ.

【0006】[0006]

【課題を解決するための手段】上記目的を達成するため
に、本発明の電解液は、エチレングリコールまたはエチ
レングリコールとγ‐ブチロラクトンを混合した溶媒
に、安息香酸カリウムおよびギ酸カリウムと、その他の
添加物を加えて溶解させたものである。
In order to achieve the above object, the electrolytic solution of the present invention comprises a solvent in which ethylene glycol or ethylene glycol and γ-butyrolactone are mixed, potassium benzoate and potassium formate, and other additives. It is a product added and dissolved.

【0007】溶媒として従来の水に代えて、沸点が20
3℃と高いγ‐ブチロラクトンをエチレングリコールに
混合することにより、電解液の揮散を抑えて温度105
℃〜125℃という高温下での耐熱性を得ることができ
る。
Instead of conventional water as a solvent, the boiling point is 20
By mixing γ-butyrolactone as high as 3 ° C with ethylene glycol, the volatilization of the electrolytic solution is suppressed and the temperature is kept at 105
It is possible to obtain heat resistance at a high temperature of ℃ to 125 ℃.

【0008】溶質として有機酸塩の中でも高温下で安定
な安息香酸のカリウム塩を使用することにより溶質の分
解並びにガス発生を防ぐことができる。
Among the organic acid salts, the potassium salt of benzoic acid, which is stable at high temperature, is used as the solute, whereby the decomposition of solute and the generation of gas can be prevented.

【0009】また有機酸カリウムである安息香酸カリウ
ム1種のみからなる電解液は比抵抗値が高いのみならず
pHが高くなり、化成性が低下するため、カリウム塩の
中でも相当に解離度の高いギ酸カリウムを加えて、電解
液の比抵抗値を下げるとともに、ギ酸、アジピン酸、コ
ハク酸、安息香酸のうち、いずれか1種の酸を加えてp
H値を下げ、化成性を向上せしめる。
Further, an electrolytic solution containing only one kind of potassium benzoate, which is an organic acid potassium, has not only a high specific resistance value but also a high pH and a low chemical conversion property, and therefore the dissociation degree is considerably high among the potassium salts. Add potassium formate to reduce the specific resistance of the electrolyte and add one of formic acid, adipic acid, succinic acid and benzoic acid to add p.
Lowers the H value and improves chemical conversion.

【0010】さらに少量の亜リン酸を添加して陽極酸化
皮膜の安定化を図る。
Further, a small amount of phosphorous acid is added to stabilize the anodized film.

【0011】すなわち本発明は、エチレングリコールを
主体とする溶媒か、またはエチレングリコールにγ‐ブ
チロラクトン0.1〜30.0重量% を混合した溶媒
に安息香酸カリウム1.0〜10.0重量% およびギ
酸カリウム1.0〜10.0重量% 、およびギ酸、ア
ジピン酸、コハク酸、安息香酸の何れか1種を0.3〜
3.0重量% 、亜リン酸0.1〜0.3重量% を溶解
したことを特徴とする電解コンデンサの駆動用電解液で
ある。
That is, according to the present invention, a solvent mainly comprising ethylene glycol or a solvent obtained by mixing 0.1 to 30.0% by weight of γ-butyrolactone with ethylene glycol is added to 1.0 to 10.0% by weight of potassium benzoate. And 1.0 to 10.0% by weight of potassium formate, and 0.3 to 1 of any one of formic acid, adipic acid, succinic acid and benzoic acid.
This is an electrolytic solution for driving an electrolytic capacitor in which 3.0% by weight and 0.1 to 0.3% by weight of phosphorous acid are dissolved.

【0012】[0012]

【作用】本発明で使用する溶媒の沸点が高いので、電解
液の高温下での揮散を抑えることができる。また、溶質
として使用する安息香酸カリウムは、電解コンデンサの
高温での寿命特性を長期に安定化させるものであるが、
その作用としては、安息香酸カリウムを形成するベンゼ
ン核が高温下で安定なことによるものと考えられる。加
えて、有機酸のアンモニウム塩では、高温下で分解し、
アンモニアガスとして散逸するのに対し、有機酸のカリ
ウム塩ではそのおそれがなく、高温下で安定した寿命特
性が得られる。なお、ギ酸カリウム量は1.0重量%
未満では電解液の比抵抗値を充分に下げられず、また1
0.0重量% を超えると電解液の火花電圧が低下す
る。そして、安息香酸カリウム量は1.0重量% 未満
では高温での安定性が低下し、また10.0重量% を
超えると、低温での導電度が悪化する。また、ギ酸、ア
ジピン酸、コハク酸、安息香酸の4種の酸のうち、いず
れか1種の酸の添加量は0.3重量% 未満では化成性
の促進効果が少なく、化成能力の改善とはならず、また
3.0重量% を超えると低温での導電度が悪化する。
さらに亜リン酸の添加量は0.1重量% 未満では陽極
酸化皮膜の安定化作用が少なく、0.3重量% を超え
ると高温寿命試験特性が悪化する。なお、溶媒について
はγ‐ブチロラクトンを0.1重量% 以上添加すれ
ば、低温特性をより改善できるが、その含有量が30.
0重量% を超えると、高温寿命試験特性が悪化する。
また、γ−ブチロラクトンを加えない場合には、高温寿
命特性がより安定した電解コンデンサが得られる。
Since the solvent used in the present invention has a high boiling point, volatilization of the electrolytic solution at high temperatures can be suppressed. Also, potassium benzoate used as a solute stabilizes the long-term life characteristics of electrolytic capacitors at high temperatures.
It is considered that the action is due to the stability of the benzene nucleus forming potassium benzoate at high temperature. In addition, ammonium salts of organic acids decompose at high temperatures,
While it dissipates as ammonia gas, potassium salts of organic acids do not cause this, and stable life characteristics can be obtained at high temperatures. The amount of potassium formate is 1.0% by weight
If it is less than 1, the specific resistance value of the electrolyte cannot be lowered sufficiently, and 1
If it exceeds 0.0% by weight, the spark voltage of the electrolytic solution decreases. When the amount of potassium benzoate is less than 1.0% by weight, the stability at high temperature is lowered, and when it exceeds 10.0% by weight, the conductivity at low temperature is deteriorated. Further, if the addition amount of any one of the four kinds of acids of formic acid, adipic acid, succinic acid and benzoic acid is less than 0.3% by weight, the effect of promoting the chemical conversion is small and the chemical conversion ability is improved. If it exceeds 3.0% by weight, the conductivity at low temperature deteriorates.
Further, if the addition amount of phosphorous acid is less than 0.1% by weight, the stabilizing effect of the anodized film is small, and if it exceeds 0.3% by weight, the high temperature life test characteristics deteriorate. Regarding the solvent, the low-temperature characteristics can be further improved by adding γ-butyrolactone in an amount of 0.1% by weight or more, but its content is 30.
When it exceeds 0% by weight, the high temperature life test characteristics are deteriorated.
Moreover, when γ-butyrolactone is not added, an electrolytic capacitor having more stable high temperature life characteristics can be obtained.

【0013】[0013]

【実施例】以下、本発明の実施例について説明する。表
1は、本発明の電解液と従来の電解液の組成、比抵抗、
pH、および火花発生電圧についての比較例を示す。図
1〜2には、本発明の電解液 試料番号14および17
と従来の電解液試料番号1を用いて、定格10V,47
0μFおよび定格50V,33μFの電解コンデンサを
作製し、高温負荷寿命試験(125℃定格電圧印加)を
行った結果を示す。図1は定格10V,470μFの電
解コンデンサの高温負荷寿命試験特性図 図2は定格50V,33μFの電解コンデンサの高温負
荷寿命試験特性図で、各図の(イ)は漏れ電流、(ロ)
は損失角の正接(tanδ)、(ハ)は静電容量変化率
の経時変化を示す。また、図中a,bは各々、本発明の
電解液試料番号14および17を用いた電解コンデン
サ、cは従来の電解液試料番号1を用いた電解コンデン
サである。図1〜2から明らかなように、本発明の電解
液を用いた電解コンデンサ(a、b)は従来の電解液を
用いた電解コンデンサ(c)に比べ、高温中における静
電容量変化およびtanδ変化が大幅に改善されてい
る。
EXAMPLES Examples of the present invention will be described below. Table 1 shows the compositions of the electrolytic solution of the present invention and the conventional electrolytic solution, the specific resistance,
Comparative examples of pH and spark generation voltage will be shown. 1-2, electrolyte solutions of the present invention, sample numbers 14 and 17
And the conventional electrolyte sample No. 1 were used, rated 10V, 47
The results obtained by producing an electrolytic capacitor of 0 μF and a rating of 50 V and 33 μF and performing a high temperature load life test (125 ° C. rated voltage application) are shown. Fig. 1 is a high temperature load life test characteristic diagram of an electrolytic capacitor rated at 10V and 470µF. Fig. 2 is a high temperature load life test characteristic diagram of an electrolytic capacitor rated at 50V and 33µF. In each figure, (a) shows leakage current and (b) shows.
Represents the tangent (tan δ) of the loss angle, and (c) represents the change with time of the capacitance change rate. Further, in the figure, a and b are electrolytic capacitors using the electrolytic solution sample numbers 14 and 17 of the present invention, and c is an electrolytic capacitor using the conventional electrolytic solution sample number 1. As is clear from FIGS. 1 and 2, the electrolytic capacitor (a, b) using the electrolytic solution of the present invention has a capacitance change and tan δ at high temperature as compared with the electrolytic capacitor (c) using the conventional electrolytic solution. The changes have been greatly improved.

【0014】[0014]

【表1】 [Table 1]

【0015】[0015]

【発明の効果】以上のように本発明の電解液は、高温下
で安定な安息香酸カリウムを使用しており、また、併用
するギ酸カリウムも高温下で分解するおそれがないこと
に加えて、使用する有機溶媒の沸点も高いので、電解液
の揮散が起こりにくくなり、高温中における電解コンデ
ンサの静電容量変化およびtanδ変化を改善すること
ができるものである。
As described above, the electrolytic solution of the present invention uses potassium benzoate which is stable at high temperature, and the potassium formate used in combination does not decompose at high temperature. Since the boiling point of the organic solvent used is high, the volatilization of the electrolytic solution is less likely to occur, and the change in capacitance and change in tan δ of the electrolytic capacitor at high temperature can be improved.

【図面の簡単な説明】[Brief description of drawings]

【図1】定格10V,470μFの電解コンデンサの高
温負荷寿命試験特性図
FIG. 1 High temperature load life test characteristic diagram of electrolytic capacitor rated at 10V and 470μF

【図2】定格50V,33μFの電解コンデンサの高温
負荷寿命試験特性図
FIG. 2 High temperature load life test characteristic diagram of electrolytic capacitor rated 50V, 33μF

Claims (2)

(57)【特許請求の範囲】(57) [Claims] 【請求項1】 エチレングリコールを主体とする溶媒に
安息香酸カリウム1.0〜10.0重量% およびギ酸
カリウム1.0〜10.0重量% 、およびギ酸、アジ
ピン酸、コハク酸、安息香酸の何れか1種を0.3〜
3.0重量% 、亜リン酸0.1〜0.3重量% を溶解
したことを特徴とする電解コンデンサの駆動用電解液。
1. A solvent comprising ethylene glycol as a main component, containing 1.0 to 10.0% by weight of potassium benzoate and 1.0 to 10.0% by weight of potassium formate, and containing formic acid, adipic acid, succinic acid and benzoic acid. Any one of 0.3 ~
An electrolytic solution for driving an electrolytic capacitor, wherein 3.0% by weight and 0.1 to 0.3% by weight of phosphorous acid are dissolved.
【請求項2】 溶媒としてγ−ブチロラクトンを0.1
〜30.0重量%添加したことを特徴とする請求項1の
電解コンデンサの駆動用電解液。
2. γ-butyrolactone as a solvent is 0.1
The electrolytic solution for driving an electrolytic capacitor according to claim 1, wherein the electrolytic solution is added in an amount of about 30.0% by weight.
JP17231494A 1994-07-25 1994-07-25 Electrolyte for driving electrolytic capacitors Expired - Fee Related JP3487911B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP17231494A JP3487911B2 (en) 1994-07-25 1994-07-25 Electrolyte for driving electrolytic capacitors

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP17231494A JP3487911B2 (en) 1994-07-25 1994-07-25 Electrolyte for driving electrolytic capacitors

Publications (2)

Publication Number Publication Date
JPH0837132A JPH0837132A (en) 1996-02-06
JP3487911B2 true JP3487911B2 (en) 2004-01-19

Family

ID=15939624

Family Applications (1)

Application Number Title Priority Date Filing Date
JP17231494A Expired - Fee Related JP3487911B2 (en) 1994-07-25 1994-07-25 Electrolyte for driving electrolytic capacitors

Country Status (1)

Country Link
JP (1) JP3487911B2 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007073809A (en) * 2005-09-08 2007-03-22 Honda Motor Co Ltd Electric double-layer capacitor

Also Published As

Publication number Publication date
JPH0837132A (en) 1996-02-06

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