JPH0381291B2 - - Google Patents
Info
- Publication number
- JPH0381291B2 JPH0381291B2 JP20483787A JP20483787A JPH0381291B2 JP H0381291 B2 JPH0381291 B2 JP H0381291B2 JP 20483787 A JP20483787 A JP 20483787A JP 20483787 A JP20483787 A JP 20483787A JP H0381291 B2 JPH0381291 B2 JP H0381291B2
- Authority
- JP
- Japan
- Prior art keywords
- conductivity
- carbon atoms
- solute
- electrolytic
- 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
Links
- 239000003990 capacitor Substances 0.000 claims description 22
- 239000008151 electrolyte solution Substances 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 150000001450 anions Chemical class 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 6
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 5
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 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 4
- 239000002253 acid Substances 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 150000002085 enols Chemical class 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 17
- 239000003792 electrolyte Substances 0.000 description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 150000003053 piperidines Chemical class 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
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000003235 pyrrolidines Chemical class 0.000 description 3
- -1 pyrrolidinium compound Chemical class 0.000 description 3
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-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
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 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
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000011255 nonaqueous electrolyte Substances 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 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
- CVBUKMMMRLOKQR-UHFFFAOYSA-N 1-phenylbutane-1,3-dione Chemical compound CC(=O)CC(=O)C1=CC=CC=C1 CVBUKMMMRLOKQR-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
- QEELIVGPBWSYHZ-UHFFFAOYSA-N 3,3-ditert-butylpentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)(C(C)(C)C)C(C)(C)C QEELIVGPBWSYHZ-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
- 230000005856 abnormality Effects 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
- 150000001875 compounds Chemical class 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
- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical compound C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229940021013 electrolyte solution Drugs 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
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 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
- 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
- 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
誘電体層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、長期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61−61835号のように、1,3
−ジケトンのエノール型酸の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、1,3−ジケ
トン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1〜6のアルキル基ま
たはフエニル基、R3は水素、炭素数1〜6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、R5は炭素数が1〜6のアルキル基
またはアリール基、R6は水素、炭素数1〜6の
アルキル基またはアリール基)であらわされる、
1,3−ジケトン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。
次にアニオン側の1,3−ジケトンの具体例な
化合物名(〔 〕内は示性式をあらわす)を例
示すると、アセチルアセトン
〔CH3COCHCOHCH3〕、ベンゾイルアセトン
〔CH3COCHCOHC6H5〕、ジベンゾイルメタン
〔C6H5COCHCOHC6H5〕、ジ−tert−ブチル−ア
セチルアセトン〔(CH3)3CCOCHCOHC
(CH3)3〕、3−メチル−2,4−ペンタジオン
〔CH3COC(CH3)COHCH3〕などがある。
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、
1,3−ジケトンのエノール型酸からなるアニオ
ンとを組み合わせた溶質を溶媒に溶解させて電解
液を得る。
なおピロリジン誘導体、ピペリジン誘導体およ
び1,3−ジケトンは、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、エ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
どの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)/cm・30
℃である。
本発明例 1
(組成)
N,N−ジメチルピロリジウム、アセチルアセ
トネート 15
γ−ブチロラクトン 77
エチレングリコール 8
(電導度) 8.7ms
本発明例 2
(組成)
N,N−ジメチル−2−メチルピロジニウム、
3−メチル−2,4−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) 13.0ms
本発明例 3
(組成)
N,N−ジメチルピペリジニウム、ベンゾイル
アセトネート 15
N−メチルホルムアミド 85
(電導度) 18.0ms
本発明例 4
(組成)
N,N−ジメチル−2−ピペコリニウム、ジフ
エニルアセチルアセトネート 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−ジエチルピペリジニウム、ジ−tert−
ブチルアセチルアセトネート 15
N−メチルホルムアミド 60
N,N−ジメチルホルムアミド 25
(電導度) 13.7ms
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 electrolyte is interposed between the dielectric layer of the electrolytic capacitor and the collector cathode, and the resistance of the electrolyte is inserted in series with the electrolytic capacitor, so if the conductivity of the electrolyte is low, By increasing the equivalent series resistance inside the electrolytic capacitor,
It has the disadvantage of 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. This had the drawback of increasing vapor pressure, causing 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, as disclosed in Japanese Patent Application No. 61-61835,
-The present inventors have proposed a method using a quaternary ammonium salt of an enol-type acid of a diketone as a solute, and a method using a carboxylate of a pyrrolidinium compound or a piperidinium compound as a solute, as in Japanese Patent Application No. 62-51885. However, the present inventor further proposed in the present invention that a solute that provides such high conductivity is a solute that has a cation of quaternary ammonium of a pyrrolidine derivative or a piperidine derivative and an anion of 1,3-diketone. It has been found that it is suitable for the purpose of [Means for solving the problem] The electrolytic solution of the present invention has the general formula: (wherein, R 1 and R 2 are alkyl groups having 1 to 6 carbon atoms or phenyl groups, R 3 is hydrogen, alkyl groups having 1 to 6 carbon atoms, and n is 4 or 5), a pyrrolidine derivative or piperidine The quaternary ammonium derivative is used as a cation, and the general formula is (wherein R 4 and R 5 are an alkyl group or an aryl group having 1 to 6 carbon atoms, R 6 is hydrogen, an alkyl group or an aryl group having 1 to 6 carbon atoms),
The electrolytic solution is characterized by containing a solute having an enol-type acid of 1,3-diketone as an anion. 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. Next, specific example compound names of 1,3-diketones on the anion side (the numbers in parentheses represent an indicative formula) are as follows: acetylacetone [CH 3 COCHCOHCH 3 ], benzoylacetone [CH 3 COCHCOHC 6 H 5 ], Dibenzoylmethane [C 6 H 5 COCHCOHC 6 H 5 ], di-tert-butyl-acetylacetone [(CH 3 ) 3 CCOCHCOHC
( CH3 ) 3 ], 3-methyl-2,4-pentadione [ CH3COC ( CH3 ) COHCH3 ], and the like. A quaternary ammonium cation obtained from these pyrrolidine derivatives or piperidine derivatives,
An electrolytic solution is obtained by dissolving a solute in combination with an anion consisting of an enol type acid of 1,3-diketone in a solvent. Note that the pyrrolidine derivatives, piperidine derivatives, and 1,3-diketones 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, exylene glycol, phenyl glycol, glycerin, methyl cellosolve, and N-methyl-2-pyrrolidone, dimethyl sulfoxide, Various solvents such as acetonitrile can be mentioned. 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 % by weight, and electrical conductivity is ms (milliSiemens)/cm・30
It is ℃. Present invention example 1 (Composition) N,N-dimethylpyrrolidium, acetylacetonate 15 γ-butyrolactone 77 Ethylene glycol 8 (Conductivity) 8.7ms Present invention example 2 (Composition) N,N-dimethyl-2-methylpyrrolidium nium,
3-Methyl-2,4-pentanedionate 15 N,N-dimethylformamide 77 Ethylene glycol 8 (Conductivity) 13.0ms Invention example 3 (Composition) N,N-dimethylpiperidinium, benzoylacetonate 15 N- Methylformamide 85 (Conductivity) 18.0ms Invention Example 4 (Composition) N,N-dimethyl-2-pipecorinium, diphenylacetylacetonate 15 Acetonitrile 60 γ-butyrolactone 25 (Conductivity) 14.3ms Invention Example 5 (Composition) ) N,N-diethylpiperidinium, di-tert-
Butylacetylacetonate 15 N-methylformamide 60 N,N-dimethylformamide 25 (Conductivity) 13.7ms Comparative example (Composition) Ammonium adipate 12 Ethylene glycol 78 Water 10 (Conductivity) 6.7ms As shown in the above results, It can be seen that the electrolytic solution of the present invention exhibits higher conductivity than the conventional electrolytic solution. 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.
【表】
この試験の結果からも明らかなように、本発明
の電解液の電導度が高いことから、従来のものに
比べ損失すなわちtanδの値が低くなる。
また、本質的に水を含まないので高温負荷状態
に置いても、内圧上昇による外観異常や静電容量
の減少等がなく、初期値と1000時間後の特性値の
比較においても、この発明のものは極めて変化が
少ない。
〔発明の効果〕
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
で長期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。[Table] As is clear from the results of this test, since the electrolytic solution of the present invention has a high conductivity, the loss, that is, the tan δ value, is lower than that of the conventional electrolytic solution. In addition, since it essentially does not contain water, there is no appearance abnormality or decrease in capacitance due to increased internal pressure even when placed under high-temperature load conditions, and a comparison of initial values and characteristic values after 1000 hours shows that this invention Things change very little. [Effects of the Invention] 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 for a long time at high temperatures, so it can be used at high frequencies. Moreover, it can exhibit excellent characteristics when used in power supplies such as switching regulators that require high efficiency, and various electrical devices that are used at high temperatures for long periods of time.
Claims (1)
たはフエニル基、R3は水素、炭素数1〜6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、R5は炭素数1〜6のアルキル基ま
たはアリール基、R6は水素、炭素数1〜6のア
ルキル基またはアリール基)であらわされる、
1,3−ジケトンのエノール型酸をアニオンとす
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 (wherein R 1 and R 2 are alkyl groups having 1 to 6 carbon atoms or phenyl groups, R 3 is hydrogen or an alkyl group having 1 to 6 carbon atoms, and n is 4 or 5), a pyrrolidine derivative or piperidine Using the derivative quaternary ammonium as a cation, the general formula (wherein R 4 and R 5 are an alkyl group or an aryl group having 1 to 6 carbon atoms, R 6 is hydrogen, an alkyl group or an aryl group having 1 to 6 carbon atoms),
An electrolytic solution for an electrolytic capacitor, characterized in that it contains a solute having an enol type acid of 1,3-diketone as an anion.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP20483787A JPS6447012A (en) | 1987-08-18 | 1987-08-18 | Electrolyte for electrolytic condenser |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP20483787A JPS6447012A (en) | 1987-08-18 | 1987-08-18 | Electrolyte for electrolytic condenser |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6447012A JPS6447012A (en) | 1989-02-21 |
JPH0381291B2 true JPH0381291B2 (en) | 1991-12-27 |
Family
ID=16497209
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP20483787A Granted JPS6447012A (en) | 1987-08-18 | 1987-08-18 | Electrolyte for electrolytic condenser |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6447012A (en) |
Families Citing this family (2)
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 |
CN107680811A (en) * | 2017-11-18 | 2018-02-09 | 陈馨雅 | A kind of electrolyte for aluminum electrolytic capacitor |
-
1987
- 1987-08-18 JP JP20483787A patent/JPS6447012A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS6447012A (en) | 1989-02-21 |
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