JPH0416932B2 - - Google Patents
Info
- Publication number
- JPH0416932B2 JPH0416932B2 JP20483987A JP20483987A JPH0416932B2 JP H0416932 B2 JPH0416932 B2 JP H0416932B2 JP 20483987 A JP20483987 A JP 20483987A JP 20483987 A JP20483987 A JP 20483987A JP H0416932 B2 JPH0416932 B2 JP H0416932B2
- Authority
- JP
- Japan
- Prior art keywords
- conductivity
- electrolytic
- methyl
- solute
- composition
- 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
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- 239000003990 capacitor Substances 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 150000001450 anions Chemical class 0.000 claims description 7
- 150000001768 cations Chemical class 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 150000003053 piperidines Chemical class 0.000 claims description 5
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- FKCMADOPPWWGNZ-YUMQZZPRSA-N [(2r)-1-[(2s)-2-amino-3-methylbutanoyl]pyrrolidin-2-yl]boronic acid Chemical compound CC(C)[C@H](N)C(=O)N1CCC[C@H]1B(O)O FKCMADOPPWWGNZ-YUMQZZPRSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 21
- 239000008151 electrolyte solution Substances 0.000 description 13
- 239000003792 electrolyte Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 6
- -1 pyrrolidinium compound Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- PMDCZENCAXMSOU-UHFFFAOYSA-N N-ethylacetamide Chemical compound CCNC(C)=O PMDCZENCAXMSOU-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- 239000011255 nonaqueous electrolyte Substances 0.000 description 2
- 150000003235 pyrrolidines Chemical class 0.000 description 2
- BAJXCBJYFBUTCH-UHFFFAOYSA-N 1,1,2-trimethylpyrrolidin-1-ium Chemical compound CC1CCC[N+]1(C)C BAJXCBJYFBUTCH-UHFFFAOYSA-N 0.000 description 1
- DLXKCYABLDYCPZ-UHFFFAOYSA-N 1,1,3-trimethylpyrrolidin-1-ium Chemical compound CC1CC[N+](C)(C)C1 DLXKCYABLDYCPZ-UHFFFAOYSA-N 0.000 description 1
- HNVRIVKDRYGTED-UHFFFAOYSA-N 1,1-diethylpiperidin-1-ium Chemical compound CC[N+]1(CC)CCCCC1 HNVRIVKDRYGTED-UHFFFAOYSA-N 0.000 description 1
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- HSPCIUQMOOXJQU-UHFFFAOYSA-N 5,5-dimethylcyclohexane-1,3-dicarboxylic acid Chemical compound CC1(C)CC(C(O)=O)CC(C(O)=O)C1 HSPCIUQMOOXJQU-UHFFFAOYSA-N 0.000 description 1
- FLDCSPABIQBYKP-UHFFFAOYSA-N 5-chloro-1,2-dimethylbenzimidazole Chemical compound ClC1=CC=C2N(C)C(C)=NC2=C1 FLDCSPABIQBYKP-UHFFFAOYSA-N 0.000 description 1
- 239000001741 Ammonium adipate Substances 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
- HTLZVHNRZJPSMI-UHFFFAOYSA-N N-ethylpiperidine Chemical compound CCN1CCCCC1 HTLZVHNRZJPSMI-UHFFFAOYSA-N 0.000 description 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 235000019293 ammonium adipate Nutrition 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- IBTMICNUANPMIH-UHFFFAOYSA-N diazanium ethane-1,2-diol hexanedioate Chemical compound C(CO)O.C(CCCCC(=O)[O-])(=O)[O-].[NH4+].[NH4+] IBTMICNUANPMIH-UHFFFAOYSA-N 0.000 description 1
- 125000004989 dicarbonyl group Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229940021013 electrolyte solution Drugs 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- NNCAWEWCFVZOGF-UHFFFAOYSA-N mepiquat Chemical compound C[N+]1(C)CCCCC1 NNCAWEWCFVZOGF-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- KERBAAIBDHEFDD-UHFFFAOYSA-N n-ethylformamide Chemical compound CCNC=O KERBAAIBDHEFDD-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000003386 piperidinyl group Chemical group 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Pyrrole Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Description
〔産業上の利用分野〕
この発明は、電解コンデンサ用の電解液の改良
に関するものである。
〔従来の技術〕
電解コンデンサは、アルミニウム、タンタルな
どの表面に絶縁性の酸化皮膜が形成されるいわゆ
る弁金属を陽極電極に使用し、前記酸化皮膜層を
誘電体とし、この酸化皮膜層の表面に電解質層と
なる電解液を接触させ、さらに通常陰極と称する
集電用の電極を配置して構成されている。
電解コンデンサ用電解液は、上述したように誘
電体層に直接接触し、真の陰極として作用するこ
とから、そ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。電解液は電解コンデンサの
誘電体と集電陰極との間に介在して、電解液の抵
抗分が電解コンデンサに直列に挿入されているこ
とになるので、電解液の電導度が低いと、電解コ
ンデンサの内部の等価直列抵抗分を増大させ、高
周波特性や損失特性が悪くなる欠点がある。
このような背景から電導度の高い電解液が求め
られており、従来から、電導度の高い電解液とし
て、アジピン酸などの有機酸またはその塩をエチ
レングリコールなどのグリコール類やアルコール
類に溶解したものが用いられている。
ところで、近年ますます高度の電気的特性の電
解コンデンサが求められており、現状の電解液の
電導度では十分とはいえない。特に現状の電解液
の場合、所望の電導度が得られない場合や溶解度
が低い溶質を用いたときなどは、意図的に水を添
加して電導度の向上を図ることがおこなわれてい
る。
しかしながら、最近のように100℃を越える高
温度下で長時間の使用が求められる電解コンデン
サの使用状況においては、電解液中の水分の存在
は、誘電体皮膜層の劣化や、電解コンデンサの内
部蒸気圧を高め、封口部の破損や電解液の蒸散に
よる寿命劣化を招き、長時間にわたつて安定した
特性を維持できない欠点があつた。
〔発明が解決しようとする問題点〕
この発明は、従来の電解液の上述したような欠
点を改善したもので、非水系でかつ高導電度を与
える電解液を得ることにより、電解コンデンサの
電気的特性を向上させ、かつ安定した特性を長期
間維持することによつて電解コンデンサの信頼性
を向上させることを目的としている。
このような非水系で高電導度の電解液として
は、例えば特願昭61−65331号のように、環状β
−ジカルボニル化合物の４級アンモニウム塩を溶
質に用いたものや、特願昭62−51885号のように、
ピロリジニウム化合物またはピペリジニウム化合
物のカルボン酸塩を溶質として用いたものが本発
明者らから提案されているが、本発明者は、さら
にこのような高電導度を与える溶質として、ピロ
リジン誘導体またはピペリジン誘導体の４級アン
モニウムをカチオンとし、環状β−ジカルボニル
化合物をアニオンとした溶質がこの発明の目的に
適合することを見出したものである。
〔問題点を解決するための手段〕
この発明の電解液は、一般式が、
（式中、R1，R2は炭素数１ないし６のアルキル
基またはフエニル基、R3は水素または炭素数１
ないし６のアルキル基、ｎは４または５）であら
わされる、ピロリジン誘導体またはピペリジン誘
導体の４級アンモニウムをカチオンとし、
さらに一般式が、
（式中、R4は水素または炭素数１ないし６のア
ルキル基、ｍは２ないし５）であらわされる、環
状β−ジカルボニル化合物のエノール型酸をアニ
オンとした溶質を含むことを特徴とした電解液で
ある。
この発明の溶質のカチオン側には、ピロリジン
誘導体またはピペリジン誘導体の窒素原子に、ア
ルキル基あるいはフエニル基などが結合して共有
結合原子価４のカチオン形成し、ピロリジンまた
はピペリジン環の窒素が４級アンモニウムの形と
なつたものが用いられる。
この中でピロリジン誘導体について例示する
と、
Ｎ−メチル−ピロリジン
Ｎ−メチル−２−メチルピロリジン
Ｎ−メチル−３−メチルピロリジン
などがある。
またピペリジン誘導体については、
Ｎ−メチル−ピペリジン
Ｎ−メチル−２−ピペコリン
Ｎ−メチル−３−ピペコリン
Ｎ−メチル−４−ピペコリン
Ｎ−エチル−ピペリジン
などの誘導体を例示することができる。
一方アニオン側の環状β−ジカルボニル化合物
の具体例な化合物名についても、具体的なものを
例示とすると、
１，３−シクロペンタンジオン
２−メチル−１，３−シクロペンタンジオン
１，３−シクロヘキサンジオン
２−メチルシクロヘキサン−１，３−ジオン
５，５−ジメチル−１，３−シクロヘキサンジ
オン
などをあげることができる。
これらピロリジン誘導体またはピペリジン誘導
体から得られる４級アンモニウムのカチオンと、
β−ジカルボニル化合物のエノール型酸のアニオ
ンとを組み合わせた溶質を溶媒に溶解して電解液
を得る。
なお、カチオン側化合物、アニオン側化合物は
これら例示したものに限定されるものではない。
また、この発明で用いることのできる溶媒は、
実質的に水を含まない非水溶媒であれば、特に限
定はなく、各種の非プロトン溶媒、プロトン溶媒
あるいはこれらの混合系の溶媒を用いることがで
きる。
この発明で用いることのできる溶媒を例示する
と、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な
どの酸アミド類、γ−ブチロラクトン、γ−バレ
ロラクトンなどのラクトン類、エチレンカーボネ
ート、ブチレンカーボネート、プロピレンカーボ
ネートなどのカーボネート類、エチレングリコー
ル、ジエチレングリコール、プロピレングリコー
ル、ヘキシレングリコール、フエニルグリコー
ル、グリセリン、メチルセロソルブなどの多価ア
ルコール類、さらには、Ｎ−メチル−２−ピロリ
ドン、ジメチルスルホキシド、アセトニトリルな
ど、各種の溶媒をあげることができる。
なおこれらの溶媒は、一種のみの使用に限定さ
れるものではなく、二種あるいはそれ以上の混合
物であつてもよい。溶媒の選択は、使用する溶質
の溶解度や使用温度範囲などを考慮して決定すれ
ばよい。
〔作用〕
この発明の溶質を溶解した電解液は、電導度が
従来のものに比べて高いので、電解コンデンサに
用いたとき、電解コンデンサ内部の抵抗分が減少
し、損失の低減など電気特性が向上する。
また水を本質的に含まないので、高温度での使
用において、水蒸気などを発生させるおそれがな
い。
〔実施例〕
以下実施例に基いて、この発明を説明する。
まず、この発明の実施例として、この発明のカ
チオンおよびアニオンを組み合わせた溶質溶媒中
に溶解して電解液を作成し、その電導度を調べ
た。
なお従来例として、従来から高い電導度を示す
アジピン酸アンモニウム−エチレングリコール系
の電解液と比較した。この組成ならびに、電導度
を以下のとおり示す。なお組成割合はいずれも重
量％、電導度はｍｓ（ミリジーメンス）／mm・30
℃である。
本発明例 １
（組成）
Ｎ，Ｎ−ジメチルピロリジウム、５，５−ジメチ
ル−１，３−シクロヘキサンジオネート 15
γ−ブチロラクトン 77
エチレングリコール ８
（電導度） 7.1ｍｓ
本発明例 ２
（組成）
Ｎ，Ｎ−ジメチル−２−メチルピロリジニウム、
１，３−シクロペンタンジオネート 15
Ｎ，Ｎ−ジメチルホルムアミド 77
エチレングリコール ８
（電導度） 10.0ｍｓ
本発明例 ３
（組成）
Ｎ，Ｎ−ジメチル−３−メチルピロリジニウム、
２−メチル−１，３−シクロペンタンジオネート
15
Ｎ−メチルホルムアミド 85
（電導度） 12.5ｍｓ
本発明例 ４
（組成）
Ｎ，Ｎ−メチルエチルピロリジニウム、１，３−
シクロヘキサンジオネート 15
アセトニトリル 60
γ−ブチロラクトン 25
（電導度） 14.3ｍｓ
本発明例 ５
（組成）
Ｎ，Ｎ−ジメチルピペリジニウム、５，５−ジメ
チル−１，３−シクロヘキサンジオネート 15
γ−ブチロラクトン 77
エチレングリコール ８
（電導度） 7.2ｍｓ
本発明例 ６
（組成）
Ｎ，Ｎ−ジメチル−２−ピペコリン、１，３−シ
クロペンタンジオネート 15
Ｎ，Ｎ−ジメチルホルムアミド 77
エチレングリコール ８
（電導度） 10.3ｍｓ
本発明例 ７
（組成）
Ｎ，Ｎ−ジエチルピペリジニウム、２−メチル−
１，３−シクロペンタンジオネート 15
Ｎ−メチルホルムアミド 85
（電導度） 12.8ｍｓ
本発明例 ８
（組成）
Ｎ，Ｎ−メチルエチル−３−ピペコリン、２−メ
チルシクロヘキサン−１，３−ジオネート 15
アセトニトリル 60
γ−ブチロラクトン 25
（電導度） 14.6ｍｓ
比較例
（組成）
アジピン酸アンモニウム 12
エチレングリコール 78
水 10
（電導度） 6.7ｍｓ
以上の結果のように、この発明の電解液は、従
来のものに比べて高い電導度を示していることが
わかる。
次にこれらの電解液を用いて電解コンデンサを
製作し、その特性の比較をおこなつた。
製作した電解コンデンサは、アルミニウム箔を
陽極ならびに陰極に用い、セパレータ紙を挟んで
重ね合わせて巻回して円筒状のコンデンサ素子と
したものに、各実施例の電解液を含浸して外装ケ
ースに収納して密封したものである。
いずれも同一のコンデンサ素子を用いており、
定格電圧16V定格容量180μFのものである。
以下の表は、これら電解コンデンサの初期値な
らびに110℃で定格電圧を印加して1000時間経過
後の静電容量値（CAP）、損失角の正接（tanδ）、
漏れ電流値（LC）（２分値）をあらわしている。
なおこれらの測定値はいずれの実施例も製品10
個の測定値の平均である。
[Industrial Field of Application] This invention relates to improvement of electrolyte solutions for electrolytic capacitors. [Prior Art] Electrolytic capacitors use a valve metal such as aluminum or tantalum on the surface of which an insulating oxide film is formed for the anode electrode.The oxide film layer is used as a dielectric, and the surface of this oxide film layer is It is constructed by bringing an electrolytic solution which forms an electrolyte layer into contact with the electrode, and further arranging a current collecting electrode, which is usually called a cathode. As described above, the electrolytic solution for an electrolytic capacitor comes into direct contact with the dielectric layer and acts as a true cathode, so its properties are a major factor influencing the properties of the electrolytic capacitor. The electrolytic solution is interposed between the dielectric of the electrolytic capacitor and the collector cathode, and the resistance of the electrolytic solution is inserted in series with the electrolytic capacitor, so if the conductivity of the electrolytic solution is low, the electrolytic This has the disadvantage that it increases the equivalent series resistance inside the capacitor, resulting in poor high frequency characteristics and loss characteristics. Against this background, there is a demand for electrolytes with high conductivity, and conventionally, electrolytes with high conductivity have been prepared by dissolving organic acids such as adipic acid or their salts in glycols such as ethylene glycol or alcohols. something is being used. Incidentally, in recent years, electrolytic capacitors with increasingly sophisticated electrical characteristics have been required, and the current conductivity of the electrolytic solution is not sufficient. Particularly in the case of current electrolytes, when the desired conductivity cannot be obtained or when a solute with low solubility is used, water is intentionally added to improve the conductivity. However, in recent years, when electrolytic capacitors are used for long periods of time at high temperatures exceeding 100°C, the presence of moisture in the electrolyte can cause deterioration of the dielectric film layer and the inside of the electrolytic capacitor. The drawback was that it increased the vapor pressure, leading to damage to the sealing part and deterioration of life due to evaporation of the electrolyte, and the inability to maintain stable characteristics over a long period of time. [Problems to be Solved by the Invention] The present invention improves the above-mentioned drawbacks of conventional electrolytes. By obtaining a non-aqueous electrolyte that provides high conductivity, the present invention improves the electrical performance of electrolytic capacitors. The objective is to improve the reliability of electrolytic capacitors by improving their physical characteristics and maintaining stable characteristics for a long period of time. As such a non-aqueous electrolyte with high conductivity, for example, a cyclic β electrolyte is disclosed as disclosed in Japanese Patent Application No. 61-65331.
- Those using quaternary ammonium salts of dicarbonyl compounds as solutes, and as in Japanese Patent Application No. 1985-51885,
The present inventors have proposed a method using a carboxylate of a pyrrolidinium compound or a piperidinium compound as a solute; It has been found that a solute having quaternary ammonium as a cation and a cyclic β-dicarbonyl compound as an anion is suitable for the purpose of the present invention. [Means for solving the problem] The electrolytic solution of the present invention has the general formula: (In the formula, R 1 and R 2 are an alkyl group having 1 to 6 carbon atoms or a phenyl group, and R 3 is hydrogen or a phenyl group having 1 to 6 carbon atoms.
to 6 alkyl groups, n is 4 or 5), the quaternary ammonium of a pyrrolidine derivative or a piperidine derivative is used as a cation, and the general formula is (wherein, R 4 is hydrogen or an alkyl group having 1 to 6 carbon atoms, m is 2 to 5), and is characterized by containing a solute having an anion of an enol-type acid of a cyclic β-dicarbonyl compound. It is an electrolyte. On the cation side of the solute of this invention, an alkyl group or a phenyl group is bonded to the nitrogen atom of the pyrrolidine derivative or piperidine derivative to form a covalent 4-valent cation, and the nitrogen of the pyrrolidine or piperidine ring is a quaternary ammonium. The one that takes the form of is used. Examples of pyrrolidine derivatives include N-methyl-pyrrolidine N-methyl-2-methylpyrrolidine N-methyl-3-methylpyrrolidine and so on. Regarding piperidine derivatives, N-methyl-piperidine N-methyl-2-pipecoline N-methyl-3-pipecoline N-methyl-4-pipecoline N-ethyl-piperidine Examples include derivatives such as. On the other hand, regarding the specific compound names of the cyclic β-dicarbonyl compounds on the anion side, the following are specific examples: 1,3-cyclopentanedione 2-methyl-1,3-cyclopentanedione 1,3-cyclohexanedione 2-methylcyclohexane-1,3-dione 5,5-dimethyl-1,3-cyclohexanedione etc. can be given. A quaternary ammonium cation obtained from these pyrrolidine derivatives or piperidine derivatives,
An electrolytic solution is obtained by dissolving a solute obtained by combining a β-dicarbonyl compound with an anion of an enol type acid in a solvent. Note that the cation side compound and the anion side compound are not limited to those exemplified above. Furthermore, the solvents that can be used in this invention are:
There is no particular limitation as long as it is a nonaqueous solvent that does not substantially contain water, and various aprotic solvents, protic solvents, or mixed solvents thereof can be used. Examples of solvents that can be used in this invention include N-methylformamide, N,N-dimethylformamide, N-ethylformamide, N,N
- Acid amides such as diethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-ethylacetamide, N,N-diethylacetamide, lactones such as γ-butyrolactone and γ-valerolactone, ethylene carbonate, butylene carbonate, carbonates such as propylene carbonate, polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, hexylene glycol, phenyl glycol, glycerin, methyl cellosolve, and further N-methyl-2-pyrrolidone, dimethyl sulfoxide, Various solvents can be mentioned, such as acetonitrile. Note that these solvents are not limited to the use of only one type, and may be a mixture of two or more types. The selection of the solvent may be determined in consideration of the solubility of the solute used, the operating temperature range, etc. [Function] The electrolytic solution in which the solute of the present invention is dissolved has higher conductivity than conventional ones, so when used in an electrolytic capacitor, the resistance inside the electrolytic capacitor is reduced, and electrical properties such as loss reduction are improved. improves. Furthermore, since it essentially does not contain water, there is no risk of generating water vapor when used at high temperatures. [Example] The present invention will be described below based on Examples. First, as an example of the present invention, an electrolytic solution was prepared by dissolving the cation and anion of the present invention in a solute solvent in combination, and its conductivity was examined. As a conventional example, a comparison was made with an ammonium adipate-ethylene glycol electrolyte that has conventionally shown high conductivity. The composition and conductivity are shown below. All composition ratios are weight %, and electrical conductivity is ms (milliSiemens)/mm・30
It is ℃. Present invention example 1 (Composition) N,N-dimethylpyrrolidium, 5,5-dimethyl-1,3-cyclohexanedionate 15 γ-butyrolactone 77 Ethylene glycol 8 (Electrical conductivity) 7.1 ms Present invention example 2 (Composition) N , N-dimethyl-2-methylpyrrolidinium,
1,3-Cyclopentanedionate 15 N,N-dimethylformamide 77 Ethylene glycol 8 (Conductivity) 10.0ms Invention Example 3 (Composition) N,N-dimethyl-3-methylpyrrolidinium,
2-Methyl-1,3-cyclopentanedionate
15 N-Methylformamide 85 (Conductivity) 12.5ms Invention Example 4 (Composition) N,N-methylethylpyrrolidinium, 1,3-
Cyclohexanedionate 15 Acetonitrile 60 γ-Butyrolactone 25 (Conductivity) 14.3ms Invention Example 5 (Composition) N,N-dimethylpiperidinium, 5,5-dimethyl-1,3-cyclohexanedioate 15 γ-Butyrolactone 77 Ethylene glycol 8 (Conductivity) 7.2ms Invention example 6 (Composition) N,N-dimethyl-2-pipecoline, 1,3-cyclopentanedionate 15 N,N-dimethylformamide 77 Ethylene glycol 8 (Conductivity) 10.3 ms Invention Example 7 (Composition) N,N-diethylpiperidinium, 2-methyl-
1,3-cyclopentanedionate 15 N-methylformamide 85 (conductivity) 12.8ms Invention example 8 (composition) N,N-methylethyl-3-pipecoline, 2-methylcyclohexane-1,3-dionate 15 acetonitrile 60 γ-Butyrolactone 25 (Conductivity) 14.6ms Comparative example (Composition) Ammonium adipate 12 Ethylene glycol 78 Water 10 (Conductivity) 6.7ms As shown in the above results, the electrolytic solution of this invention has a It can be seen that the conductivity is high. Next, electrolytic capacitors were manufactured using these electrolytes and their characteristics were compared. The manufactured electrolytic capacitors used aluminum foil for the anode and cathode, and rolled them overlappingly with separator paper in between to form a cylindrical capacitor element.The electrolytic solution of each example was impregnated into the capacitor element, which was then stored in an exterior case. and sealed. Both use the same capacitor element,
It has a rated voltage of 16V and a rated capacity of 180μF. The table below shows the initial values of these electrolytic capacitors, the capacitance value (CAP) after 1000 hours of applying the rated voltage at 110℃, the tangent of the loss angle (tanδ),
It represents the leakage current value (LC) (2-minute value). Note that these measured values are for product 10 in all examples.
is the average of individual measurements.
以上述べたように、この発明の電解液を用いた
電解コンデンサは、低い損失値と、高温で長時間
使用しても安定した特性が維持できるので、高い
周波数で使用され、かつ高効率が求められるスイ
ツチングレギユレータなどの電源装置や、高温度
で長時間使用される各種電気機器等に用いて優れ
た特性を発揮できる。
As described above, the electrolytic capacitor using the electrolyte of the present invention has a low loss value and can maintain stable characteristics even when used at high temperatures for long periods of time, so it is used at high frequencies and requires high efficiency. It exhibits excellent characteristics when used in power supply devices such as switching regulators, which are used for a long time, and various electrical devices that are used at high temperatures for long periods of time.
Claims (1)
基またはフエニル基、R3は水素または炭素数１
ないし６のアルキル基、ｎは４または５）であら
わされる、ピロリジン誘導体またはピペリジン誘
導体の４級アンモニウムをカチオンとし、 一般式 （式中、R4は水素または炭素数１ないし６のア
ルキル基、ｍは２ないし５）であらわされる、環
状β−ジカルボニル化合物をアニオンとする溶質
を含むことを特徴とする電解コンデンサ用電解
液。[Claims] 1. General formula (In the formula, R 1 and R 2 are an alkyl group having 1 to 6 carbon atoms or a phenyl group, and R 3 is hydrogen or a phenyl group having 1 to 6 carbon atoms.
to 6 alkyl groups, n is 4 or 5), the quaternary ammonium of a pyrrolidine derivative or a piperidine derivative is used as a cation, and the general formula (wherein R 4 is hydrogen or an alkyl group having 1 to 6 carbon atoms, and m is 2 to 5), an electrolytic capacitor characterized by containing a solute having a cyclic β-dicarbonyl compound as an anion liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20483987A JPS6447014A (en) | 1987-08-18 | 1987-08-18 | Electrolyte for electrolytic condenser |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20483987A JPS6447014A (en) | 1987-08-18 | 1987-08-18 | Electrolyte for electrolytic condenser |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6447014A JPS6447014A (en) | 1989-02-21 |
| JPH0416932B2 true JPH0416932B2 (en) | 1992-03-25 |
Family
ID=16497244
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20483987A Granted JPS6447014A (en) | 1987-08-18 | 1987-08-18 | Electrolyte for electrolytic condenser |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6447014A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019199047A1 (en) * | 2018-04-11 | 2019-10-17 | 주식회사 엘지화학 | Non-aqueous electrolyte for lithium secondary battery and lithium secondary battery comprising same |
| US11437650B2 (en) | 2018-04-11 | 2022-09-06 | Lg Energy Solution, Ltd. | Non-aqueous electrolyte solution for lithium secondary battery and lithium secondary battery including the same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4521928B2 (en) * | 2000-04-10 | 2010-08-11 | 三洋化成工業株式会社 | Electrolytic solution for electrolytic capacitor and element for electrolytic capacitor using the same |
-
1987
- 1987-08-18 JP JP20483987A patent/JPS6447014A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019199047A1 (en) * | 2018-04-11 | 2019-10-17 | 주식회사 엘지화학 | Non-aqueous electrolyte for lithium secondary battery and lithium secondary battery comprising same |
| US11437650B2 (en) | 2018-04-11 | 2022-09-06 | Lg Energy Solution, Ltd. | Non-aqueous electrolyte solution for lithium secondary battery and lithium secondary battery including the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6447014A (en) | 1989-02-21 |
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