JP4753356B2 - 電解コンデンサの駆動用電解液およびそれを用いた電解コンデンサ - Google Patents
電解コンデンサの駆動用電解液およびそれを用いた電解コンデンサ Download PDFInfo
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- JP4753356B2 JP4753356B2 JP2005161290A JP2005161290A JP4753356B2 JP 4753356 B2 JP4753356 B2 JP 4753356B2 JP 2005161290 A JP2005161290 A JP 2005161290A JP 2005161290 A JP2005161290 A JP 2005161290A JP 4753356 B2 JP4753356 B2 JP 4753356B2
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- Prior art keywords
- acid
- electrolytic capacitor
- component
- electrolytic solution
- phosphate
- Prior art date
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- 239000003792 electrolyte Substances 0.000 title claims description 7
- 239000008151 electrolyte solution Substances 0.000 claims description 43
- -1 1,2,3,4-tetramethylimidazolinium cation Chemical class 0.000 claims description 18
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 6
- 229920005604 random copolymer Polymers 0.000 claims description 5
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- 150000001768 cations Chemical class 0.000 claims description 2
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- WXUAQHNMJWJLTG-UHFFFAOYSA-N 2-methylbutanedioic acid Chemical compound OC(=O)C(C)CC(O)=O WXUAQHNMJWJLTG-UHFFFAOYSA-N 0.000 description 2
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
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- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-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
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
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- 239000000654 additive Substances 0.000 description 2
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- 125000003118 aryl group Chemical group 0.000 description 2
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- PHNWGDTYCJFUGZ-UHFFFAOYSA-N hexyl dihydrogen phosphate Chemical compound CCCCCCOP(O)(O)=O PHNWGDTYCJFUGZ-UHFFFAOYSA-N 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- QPPQHRDVPBTVEV-UHFFFAOYSA-N isopropyl dihydrogen phosphate Chemical compound CC(C)OP(O)(O)=O QPPQHRDVPBTVEV-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229960002510 mandelic acid Drugs 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- ZIYVHBGGAOATLY-UHFFFAOYSA-N methylmalonic acid Chemical compound OC(=O)C(C)C(O)=O ZIYVHBGGAOATLY-UHFFFAOYSA-N 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- MBHINSULENHCMF-UHFFFAOYSA-N n,n-dimethylpropanamide Chemical compound CCC(=O)N(C)C MBHINSULENHCMF-UHFFFAOYSA-N 0.000 description 1
- KERBAAIBDHEFDD-UHFFFAOYSA-N n-ethylformamide Chemical compound CCNC=O KERBAAIBDHEFDD-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- WYAKJXQRALMWPB-UHFFFAOYSA-N nonyl dihydrogen phosphate Chemical compound CCCCCCCCCOP(O)(O)=O WYAKJXQRALMWPB-UHFFFAOYSA-N 0.000 description 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- NVTPMUHPCAUGCB-UHFFFAOYSA-N pentyl dihydrogen phosphate Chemical compound CCCCCOP(O)(O)=O NVTPMUHPCAUGCB-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical class CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- MHZDONKZSXBOGL-UHFFFAOYSA-N propyl dihydrogen phosphate Chemical compound CCCOP(O)(O)=O MHZDONKZSXBOGL-UHFFFAOYSA-N 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 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
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003536 tetrazoles Chemical group 0.000 description 1
- 235000019303 thiodipropionic acid Nutrition 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/022—Electrolytes; Absorbents
- H01G9/035—Liquid electrolytes, e.g. impregnating materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/04—Electrodes or formation of dielectric layers thereon
- H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
- H01G9/045—Electrodes or formation of dielectric layers thereon characterised by the material based on aluminium
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Description
また、電解液の電導度は、そのままコンデンサの等価直列抵抗値に影響を与えるため、電解液の電導度を低くする試みが常になされている。
尚、このEO‐PO共重合体の平均分子量については、1000〜5000が望ましい。1000以下では蒸散性が高くなり、5000以上では比抵抗上昇が著しくなるため、好ましくない。
〔1〕有機カルボン酸類
炭素数2〜15の2〜4価のポリカルボン酸として、シュウ酸、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、アゼライン酸、セバシン酸、ウンデカン二酸、ドデカン二酸、ヘキサデカン二酸、メチルマロン酸、エチルマロン酸、ジメチルマロン酸、プロピルマロン酸、ブチルマロン酸、ペンチルマロン酸、ヘキシルマロン酸、ジメチルプロピルマロン酸、ジプロピルマロン酸、メチルコハク酸、エチルコハク酸、2,2−ジメチルコハク酸、2,3−ジメチルコハク酸、2−メチルグルタル酸、3−メチルグルタル酸、3−メチル−3−エチルグルタル酸、3,3−ジエチルグルタル酸、3−メチルアジピン酸などの飽和ポリカルボン酸、マレイン酸、フマル酸、イタコン酸、シトラコン酸などの脂肪族不飽和ポリカルボン酸、フタル酸、イソフタル酸、テレフタル酸、トリメリット酸、ピロメリット酸などの芳香族ポリカルボン酸、チオジプロピオン酸などの硫黄含有ポリカルボン酸などが例示できる。
また、炭素数2〜20のオキシカルボン酸としてグリコール酸、乳酸、ひまし油脂肪酸などの脂肪族オキシカルボン酸、サリチル酸、マンデル酸、4−ヒドロキシ−2−ナフトエ酸、3−ヒドロキシ−2−ナフトエ酸、1−ヒドロキシ−2−ナフトエ酸、6−ヒドロキシ−2−ナフトエ酸などの芳香族オキシカルボン酸が例示できる。
さらに炭素数1〜30のモノカルボン酸として、ギ酸、酢酸、プロピオン酸、酪酸、イソ酪酸、カプロン酸、エナント酸、カプリル酸、ペラルゴン酸、ミリスチン酸、ステアリン酸、ベヘン酸、ウンデカン酸などの飽和モノカルボン酸、アクリル酸、メタクリル酸、クロトン酸、オレイン酸などの不飽和モノカルボン酸、安息香酸、ケイ皮酸、ナフトエ酸、トルイル酸、エチル安息香酸、プロピル安息香酸、イソプロピル安息香酸、ブチル安息香酸、イソブチル安息香酸、第二ブチル安息香酸、第三ブチル安息香酸、ヒドロキシ安息香酸、エトキシ安息香酸、プロポキシ安息香酸、イソプロポキシ安息香酸、ブトキシ安息香酸、イソブトキシ安息香酸、第二ブトキシ安息香酸、第三ブトキシ安息香酸、アミノ安息香酸、ニトロ安息香酸などの芳香族モノカルボン酸が例示できる。
p−アルキルベンゼンスルホン酸、ノニルベンゼンスルホン酸、ドデシルベンゼンスルホン酸などのアルキルベンゼンスルホン酸類、スルホサリチル酸、メタンスルホン酸などが例示できる。
フェノール、クレゾール、キシレノール、エチルフェノール、ナフトール、シクロヘキシルフェノールなどが例示できる。
1,2,4−トリアゾール、1,2,3−トリアゾール、1,2,3−ベンゾトリアゾール、カルボキシベンゾトリアゾール、3−メルカプト−1,2,4−トリアゾール、1,2,3−トリアゾール−4,5−ジカルボン酸、3−メルカプト−5−メチル−1,2,4−トリアゾール、1,2,3,4−テトラゾールなどが例示できる。
モノメチルリン酸エステル、ジメチルリン酸エステル、モノエチルリン酸エステル、ジエチルリン酸エステル、モノプロピルリン酸エステル、ジプロピルリン酸エステル、モノイソプロピルリン酸エステル、ジイソプロピルリン酸エステル、モノブチルリン酸エステル、ジブチルリン酸エステル、モノペンチルリン酸エステル、ジペンチルリン酸エステル、モノヘキシルリン酸エステル、ジヘキシルリン酸エステル、モノヘプチルリン酸エステル、ジヘプチルリン酸エステル、モノオクチルリン酸エステル、ジオクチルリン酸エステル、モノ−2−エチルヘキシルリン酸エステル、ジ−2−エチルヘキシルリン酸エステル、モノノニルリン酸エステル、ジノニルリン酸エステル、モノデシルリン酸エステル、ジデシルリン酸エステル、モノイソデシルリン酸エステル、ジイソデシルリン酸エステルなどが例示できる。
PO4 3−、BO3 3−、F−、PF6 −、BF4 −、AsF6 −、SbF6 −、ClO−、AlF4 −、AlCl4 −、TaF6 −、NbF6 −、SiF6 2−、CN−、CNO−、F(HF)n −(nは1〜4の数値)などが例示できる。
メチルアルコール、エチルアルコール、プロピルアルコール、ブチルアルコール、ジアセトンアルコール、ベンジルアルコール、アミノアルコール、フルフリルアルコールなどの一価アルコール、エチレングリコール、プロピレングリコール、ジエチレングリコール、ヘキシレングリコールなどの二価アルコール、グリセリンなどの三価アルコール、ヘキシトールなどの四価以上のアルコールが例示できる。
エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、エチレングリコールモノフェニルエーテル、テトラヒドロフラン、3−メチルテトラヒドロフランなどのモノエーテル類、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテルなどのジエーテル類が例示できる。
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などのホルムアミド類、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アセトアミド類、N,N−ジメチルプロピオンアミドなどのプロピオンアミド類、N−メチルピロリドン、N−エチルピロリドンなどのピロリドン類が例示できる。
N−メチル−2−オキサゾリジノン、3,5−ジメチル−2−オキサゾリジノンなどが例示できる。
γ−ブチロラクトン、α−アセチル−γ−ブチロラクトン、β−ブチロラクトン、γ−バレロラクトン、δ−バレロラクトンなどが例示できる。
アセトニトリル、プロピオニトリル、ブチロニトリル、アクリロニトリル、メタクリルニトリル、ベンゾニトリルなどが例示できる。
エチレンカーボネート、プロピオンカーボネート、ブチレンカーボネート、ジメチルカーボネート、ジメチルカーボネート、ジエチルカーボネートなどが例示できる。
ジメチルスルホキシド、スルホラン、3−メチルスルホラン、2,4−ジメチルスルホランなどが例示できる。
アセトン、メチルエチルケトン、ジエチルケトン、アセトフェノン、シクロヘキサン、シクロペンタンなどが例示できる。
1,3−ジメチル−2−イミダゾリジノン、N−メチルピロリドンなどが例示できる。
アルミニウム電解コンデンサに用いる電解液として、以下の表1及び表2に記載される成分及び組成比より成るものをそれぞれ調製した。この際、成分Bの共重合体としては、EOとPOのランダム共重合体を使用した。
さらに、エッチング処理及び酸化皮膜形成処理をした陽極箔と陰極箔とをマニラ麻系のセパレータを介して巻回したコンデンサ素子を形成し、このコンデンサ素子を前記電解液に含浸した後、アルミニウムよりなる有底筒状の外装ケースに収納した。陽極及び陰極引き出しリードをブチルゴムからなる弾性封口体に形成した貫通孔に挿入して引き出し、外装ケースの開口部には、ブチルゴムからなる弾性封口体を装着し、絞り加工により密閉して、図2に示される内部構造を有したアルミニウム電解コンデンサを作製した。
以上より、EOとPO付加mol比率は0.6:0.4〜0.8:0.2の範囲が望ましい。
以上より、水酸基価は25〜50の範囲が望ましい。
2 陰極箔
3 セパレータ
4 陽極引き出しリード
5 陰極引き出しリード
6 コンデンサ素子
7 弾性封口体
8 外装ケース
9 封口体
10 加締め(あるいは溶接)
11 陽極タブ端子
12 陰極タブ端子
13 陽極端子
14 陰極端子
15 陽極内部端子
16 陰極内部端子
17 素子固定剤
18 リード端子
19 絶縁板
Claims (2)
- 電解コンデンサを駆動させるための電解液であって、
当該電解液が、必須成分として、
成分A:イミダゾリニウム塩、
成分B:エチレンオキサイドとプロピレンオキサイドとのランダム共重合体、及び、
成分C:溶媒としてγ−ブチロラクトンを含有し、かつ、
前記成分Bにおけるエチレンオキサイドとプロピレンオキサイドの付加mol比が0.6:0.4〜0.8:0.2の範囲内であり、当該成分Bの水酸基価が25〜50であり、前記エチレンオキサイドとプロピレンオキサイドとのランダム共重合体の平均分子量が1000〜5000であり、
前記成分Aのイミダゾリニウム塩を構成するカチオンが、1,2,3,4−テトラメチルイミダゾリニウムカチオンと1−エチル−2,3−ジメチルイミダゾリニウムカチオンの少なくともいずれか一方であることを特徴とする電解コンデンサの駆動用電解液。 - 請求項1に記載の駆動用電解液を用いた電解コンデンサ。
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