JP2007123553A - Electrolyte for driving electrolytic capacitor - Google Patents
Electrolyte for driving electrolytic capacitor Download PDFInfo
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- JP2007123553A JP2007123553A JP2005313671A JP2005313671A JP2007123553A JP 2007123553 A JP2007123553 A JP 2007123553A JP 2005313671 A JP2005313671 A JP 2005313671A JP 2005313671 A JP2005313671 A JP 2005313671A JP 2007123553 A JP2007123553 A JP 2007123553A
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- Prior art keywords
- acid
- electrolytic capacitor
- electrolyte
- oxybiphenyl
- driving
- 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.)
- Granted
Links
- 239000003990 capacitor Substances 0.000 title claims abstract description 18
- 239000003792 electrolyte Substances 0.000 title abstract description 5
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- 239000002904 solvent Substances 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000008151 electrolyte solution Substances 0.000 claims description 27
- 150000003839 salts Chemical class 0.000 claims description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- 238000013329 compounding Methods 0.000 claims description 3
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- 150000003863 ammonium salts Chemical class 0.000 abstract description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 abstract description 4
- 239000004327 boric acid Substances 0.000 abstract description 4
- 239000001361 adipic acid Substances 0.000 abstract description 2
- 235000011037 adipic acid Nutrition 0.000 abstract description 2
- 150000001735 carboxylic acids Chemical class 0.000 abstract 1
- 125000002147 dimethylamino group Chemical class [H]C([H])([H])N(*)C([H])([H])[H] 0.000 abstract 1
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 18
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 9
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- 230000007423 decrease Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
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- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- OTLNPYWUJOZPPA-UHFFFAOYSA-N 4-nitrobenzoic acid Chemical compound OC(=O)C1=CC=C([N+]([O-])=O)C=C1 OTLNPYWUJOZPPA-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- NTOXAXQNZZXUQQ-UHFFFAOYSA-N C1(OC(=C(C)C)O1)=O Chemical compound C1(OC(=C(C)C)O1)=O NTOXAXQNZZXUQQ-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- MGSNFNDQSTYRDC-UHFFFAOYSA-N N-methylformamide 1-methylpyrrolidin-2-one Chemical compound C(=O)NC.CN1C(CCC1)=O MGSNFNDQSTYRDC-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- -1 acetonitrile Chemical compound 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
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Landscapes
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
Description
本発明は、電解コンデンサの駆動用電解液(以下、電解液と称す)に関するものであり、特に長期間にわたり電解コンデンサの漏れ電流を抑制できる電解液に関するものである。 The present invention relates to an electrolytic solution for driving an electrolytic capacitor (hereinafter referred to as an electrolytic solution), and particularly to an electrolytic solution that can suppress a leakage current of the electrolytic capacitor over a long period of time.
従来、電解コンデンサの漏れ電流の増大を抑制可能な電解液として、エチレングリコールを主成分とする溶媒に、アゼライン酸とホウ酸またはそのアンモニウム塩を配合した電解液に、リン酸を添加した電解液が提案されている（例えば特許文献１〜３参照）。
近年、電子機器の小形化に伴い電解コンデンサの使用環境が厳しくなり、高温でも長期間初期の電気特性を維持することが求められている。しかしながら、リン酸は、その配合量に比例して電解液の耐電圧が低下するという問題がある。その反面、リン酸の配合量を少なくすると、短期間は電解コンデンサの漏れ電流上昇を抑制できるが、長期間にわたって漏れ電流の増大を防止することができないという問題がある。 In recent years, with the miniaturization of electronic devices, the use environment of electrolytic capacitors has become severe, and it is required to maintain initial electrical characteristics for a long time even at high temperatures. However, phosphoric acid has a problem that the withstand voltage of the electrolytic solution decreases in proportion to the amount of phosphoric acid. On the other hand, if the amount of phosphoric acid is reduced, an increase in leakage current of the electrolytic capacitor can be suppressed for a short period of time, but an increase in leakage current cannot be prevented for a long period of time.
以上の問題に鑑みて、本発明の課題は、耐電圧が高く、かつ、長期間にわたって漏れ電流の増大を抑制可能な電解液を提供することにある。 In view of the above problems, an object of the present invention is to provide an electrolytic solution that has a high withstand voltage and can suppress an increase in leakage current over a long period of time.
本発明は、上記課題を解決するために各種検討した結果達成されたものであり、２−オキシビフェニルを電解液に適用することに特徴を有する。
すなわち、本発明に係る電解コンデンサの駆動用電解液では、エチレングリコールと水とを含む混合溶媒に、少なくとも、有機カルボン酸またはその塩と、ホウ酸またはその塩と多価アルコールとを配合し、以下の化学式で示される２−オキシビフェニルを配合したことを特徴とする。
The present invention has been achieved as a result of various studies to solve the above-described problems, and is characterized by applying 2-oxybiphenyl to an electrolytic solution.
That is, in the electrolytic solution for driving an electrolytic capacitor according to the present invention, at least an organic carboxylic acid or a salt thereof, boric acid or a salt thereof and a polyhydric alcohol are blended in a mixed solvent containing ethylene glycol and water. It is characterized by blending 2-oxybiphenyl represented by the following chemical formula.
本発明において、２−オキシビフェニルの配合量は、電解液全体に対して０．１〜５．０重量％であることが好ましい。 In this invention, it is preferable that the compounding quantity of 2-oxybiphenyl is 0.1 to 5.0 weight% with respect to the whole electrolyte solution.
本発明に係る電解液で用いた２−オキシビフェニルは、それを添加した際の電解液の耐電圧低下がリン酸より緩慢であるため、５．０重量％までの配合が可能となり、リン酸よりも長期間にわたって、電解コンデンサの漏れ電流の増大を防止することができる。 Since 2-oxybiphenyl used in the electrolytic solution according to the present invention has a slower withstand voltage drop than phosphoric acid when it is added, it can be blended up to 5.0% by weight. Thus, it is possible to prevent an increase in leakage current of the electrolytic capacitor over a longer period.
本発明に係る電解液では、エチレングリコールを主成分とする溶媒に、少なくとも、有機カルボン酸またはその塩と、上記の化学式で示される２−オキシビフェニルを配合したことを特徴とする。ここで、２−オキシビフェニルの配合量は、電解液全体に対して０．１〜５．０重量％であることが好ましい。また、電解液にはホウ酸またはその塩を配合することもある。 The electrolytic solution according to the present invention is characterized in that at least an organic carboxylic acid or a salt thereof and 2-oxybiphenyl represented by the above chemical formula are blended in a solvent mainly composed of ethylene glycol. Here, it is preferable that the compounding quantity of 2-oxybiphenyl is 0.1 to 5.0 weight% with respect to the whole electrolyte solution. Moreover, boric acid or its salt may be mix | blended with electrolyte solution.
本発明において、エチレングリコールに混合可能な副溶媒としては、水の他、プロピレングリコール等のグリコール類、γ−ブチロラクトン、γ−バレロラクトン、δ−バレロラクトン、Ｎ−メチル−２−ピロリドン等のラクトン類、Ｎ−メチルホルムアミド、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ−エチルホルムアミド、Ｎ，Ｎ−ジエチルホルムアミド、Ｎ−メチルアセトアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−エチルアセトアミド、Ｎ，Ｎ−ジエチルアセトアミド、ヘキサメチルホスホリックアミド等のアミド類、エチレンカーボネート、プロピレンカーボネート、イソブチレンカーボネート等の炭酸類、アセトニトリル等のニトリル類、ジメチルスルホキシド等のオキシド類、エーテル類、ケトン類、エステル類、スルホラン類等を例示することができる。 In the present invention, as a co-solvent that can be mixed with ethylene glycol, water, glycols such as propylene glycol, lactones such as γ-butyrolactone, γ-valerolactone, δ-valerolactone, and N-methyl-2-pyrrolidone N-methylformamide, N, N-dimethylformamide, N-ethylformamide, N, N-diethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-ethylacetamide, N, N-diethylacetamide, Amides such as hexamethylphosphoric amide, carbonates such as ethylene carbonate, propylene carbonate, isobutylene carbonate, nitriles such as acetonitrile, oxides such as dimethyl sulfoxide, ethers, ketones, esters, sulfolanes, etc. It can Shimesuru.
また、上記有機カルボン酸として、アゼライン酸の他、ギ酸、酢酸、アクリル酸、プロピオン酸、乳酸、酪酸、吉草酸、グルコン酸、安息香酸、ｐ−ニトロ安息香酸、アントラニル酸、サリチル酸、ゲンチシン酸、没食子酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、セバシン酸、デカンジカルボン酸、シュウ酸、トルトロン酸、フマル酸、マレイン酸、シトラコン酸、リンゴ酸、酒石酸、フタル酸、ボロジサリチル酸、クエン酸、ピロメリト酸、ナフトエ酸等が挙げられる。 In addition to azelaic acid, the organic carboxylic acid includes formic acid, acetic acid, acrylic acid, propionic acid, lactic acid, butyric acid, valeric acid, gluconic acid, benzoic acid, p-nitrobenzoic acid, anthranilic acid, salicylic acid, gentisic acid, Gallic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, decanedicarboxylic acid, oxalic acid, tolutronic acid, fumaric acid, maleic acid, citraconic acid, malic acid, tartaric acid, phthalic acid , Borodisalicylic acid, citric acid, pyromellitic acid, naphthoic acid and the like.
また、有機カルボン酸の塩として、アンモニウム塩の他、モノメチルアミン、モノエチルアミン、モノエタノールアミン、イソプロピルアミン、ｎ−プロピルアミン、ジメチルアミン、ジエチルアミン、ジエタノールアミン、ジ−ｎ−プロピルアミン、ジイソプロピルアミン、トリ−ｎ−プロピルアミン、トリメチルアミン、トリエチルアミン、トリエタノールアミン、トリ−ｎ−ブチルアミン、ジメチルエチルアミン、ナフタレンジアミン、ベンジルアミン等の塩が挙げられる。 Further, as an organic carboxylic acid salt, in addition to ammonium salt, monomethylamine, monoethylamine, monoethanolamine, isopropylamine, n-propylamine, dimethylamine, diethylamine, diethanolamine, di-n-propylamine, diisopropylamine, -N-propylamine, trimethylamine, triethylamine, triethanolamine, tri-n-butylamine, dimethylethylamine, naphthalenediamine, benzylamine and the like.
本発明に係る電解液において、２−オキシビフェニルは、それを添加した際の電解液の耐電圧低下がリン酸より緩慢であるため、５．０重量％までの配合が可能となり、リン酸よりも長期間にわたって、電解コンデンサの漏れ電流の増大を防止することができる。その理由として、２−オキシビフェニルは還元作用を有しており、陽極において２−オキシビフェニルが酸化して陽極酸化皮膜に吸着し、陽極酸化皮膜を保護するため、電解コンデンサの漏れ電流上昇を抑制できると考えられる。 In the electrolytic solution according to the present invention, since 2-oxybiphenyl has a slower withstanding voltage drop than phosphoric acid when it is added, it can be blended up to 5.0% by weight than phosphoric acid. In addition, an increase in the leakage current of the electrolytic capacitor can be prevented over a long period of time. The reason for this is that 2-oxybiphenyl has a reducing action, and 2-oxybiphenyl is oxidized at the anode and adsorbed on the anodized film to protect the anodized film, thereby suppressing an increase in leakage current of the electrolytic capacitor. It is considered possible.
以下、実施例に基づき、本発明をより具体的に説明する。 Hereinafter, based on an Example, this invention is demonstrated more concretely.
表１、表２に示す組成で電解液を調合し、８５℃における電解液の火花発生電圧（耐電圧）を測定した。そして、陽極箔と陰極箔とを電解紙を介して巻回したコンデンサ素子に電解液を含浸し、定格電圧１６０Ｖ／１５０μＦ（φ１８×２５ｍｍＬ）のアルミニウム電解コンデンサを各２０個作製し、定格電圧でエージング処理後、１０５℃−無負荷放置試験を各５個行った。 Electrolytic solutions were prepared with the compositions shown in Tables 1 and 2, and the spark generation voltage (withstand voltage) of the electrolytic solution at 85 ° C. was measured. Then, an electrolytic solution is impregnated into a capacitor element in which anode foil and cathode foil are wound through electrolytic paper, and 20 aluminum electrolytic capacitors each having a rated voltage of 160 V / 150 μF (φ18 × 25 mmL) are produced. After the aging treatment, five 105 ° C.-no-load standing tests were performed.
表１、２より分かるように、２−オキシビフェニルを配合した実施例１〜２０によれば、リン酸を添加した従来例１より、電解液の耐電圧低下を抑制でき、しかも、電解コンデンサの無負荷放置試験での漏れ電流の増大を防止することができる。
また、リン酸を３．０重量％添加した従来例２では、電解液の耐電圧が低下しており、エージング処理でショートパンクが５％発生したが、実施例では発生数は皆無であった。
As can be seen from Tables 1 and 2, according to Examples 1 to 20 in which 2-oxybiphenyl was blended, a decrease in the withstand voltage of the electrolytic solution could be suppressed as compared with Conventional Example 1 in which phosphoric acid was added. An increase in leakage current in the no-load standing test can be prevented.
Moreover, in the conventional example 2 to which 3.0% by weight of phosphoric acid was added, the withstand voltage of the electrolytic solution was lowered, and 5% of short punctures were generated by the aging treatment, but there were no occurrences in the examples. .
ここで、２−オキシビフェニルの配合量が電解液全体に対して０．１重量％未満の場合、例えば、０．０５重量％では（実施例１）、漏れ電流が増加しており、長時間の信頼性を求められる用途には不適である。また、５．０重量％を超えると、例えば６．０重量％では（実施例８）では、耐電圧が低下するため、過電圧が印加される可能性のある電解コンデンサへの適用には不適である。したがって、２−オキシビフェニルの配合量は、電解液全体に対して０．１〜５．０重量％の範囲が好ましい。 Here, when the blending amount of 2-oxybiphenyl is less than 0.1% by weight with respect to the entire electrolyte, for example, at 0.05% by weight (Example 1), the leakage current increases, and the time It is not suitable for applications that require high reliability. On the other hand, if it exceeds 5.0% by weight, for example 6.0% by weight (Example 8), the withstand voltage is lowered, so that it is not suitable for application to an electrolytic capacitor to which an overvoltage may be applied. is there. Therefore, the blending amount of 2-oxybiphenyl is preferably in the range of 0.1 to 5.0% by weight with respect to the entire electrolytic solution.
なお、本発明による２−オキシビフェニルの効果は、実施例に限定されるものではなく、先に記載した各種化合物を単独または複数配合した電解液や、副溶媒を混合した電解液に用いても、実施例と同等の効果があった。
In addition, the effect of 2-oxybiphenyl by this invention is not limited to an Example, Even if it uses for the electrolyte solution which mixed the various compounds described previously individually or in mixture, and the electrolyte solution which mixed the subsolvent. There was an effect equivalent to that of the example.
Claims (2)
2. The electrolytic solution for driving an electrolytic capacitor according to claim 1, wherein the compounding amount of 2-oxybiphenyl is 0.1 to 5.0 wt% with respect to the entire electrolytic solution.
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