JP4374459B2 - 電解コンデンサ用電解液、電解コンデンサ及び電気化学素子 - Google Patents
電解コンデンサ用電解液、電解コンデンサ及び電気化学素子 Download PDFInfo
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- JP4374459B2 JP4374459B2 JP2003345437A JP2003345437A JP4374459B2 JP 4374459 B2 JP4374459 B2 JP 4374459B2 JP 2003345437 A JP2003345437 A JP 2003345437A JP 2003345437 A JP2003345437 A JP 2003345437A JP 4374459 B2 JP4374459 B2 JP 4374459B2
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- Prior art keywords
- electrolytic
- electrolytic solution
- group
- quaternary
- salt
- 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 - Lifetime
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- 239000008151 electrolyte solution Substances 0.000 title claims description 61
- 239000003990 capacitor Substances 0.000 title claims description 52
- -1 amine salts Chemical class 0.000 claims description 42
- 150000003839 salts Chemical class 0.000 claims description 18
- 150000002500 ions Chemical class 0.000 claims description 16
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 8
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000002825 nitriles Chemical class 0.000 claims description 5
- 150000003457 sulfones Chemical class 0.000 claims description 5
- CMJLMPKFQPJDKP-UHFFFAOYSA-N 3-methylthiolane 1,1-dioxide Chemical compound CC1CCS(=O)(=O)C1 CMJLMPKFQPJDKP-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 125000000909 amidinium group Chemical group 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 150000004693 imidazolium salts Chemical group 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 150000004714 phosphonium salts Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 239000004020 conductor Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
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- 230000015572 biosynthetic process Effects 0.000 description 6
- 229940021013 electrolyte solution Drugs 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
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- WVQUCYVTZWVNLV-UHFFFAOYSA-N boric acid;oxalic acid Chemical compound OB(O)O.OC(=O)C(O)=O WVQUCYVTZWVNLV-UHFFFAOYSA-N 0.000 description 4
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- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 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
- 239000003125 aqueous solvent Substances 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- RGXROHSMPHXNNG-UHFFFAOYSA-N boric acid 2-hydroxyacetic acid oxalic acid Chemical compound OB(O)O.OCC(O)=O.OC(=O)C(O)=O RGXROHSMPHXNNG-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000004010 onium ions Chemical group 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KYRYHBRYSSBWLU-UHFFFAOYSA-N 1,2,3,4-tetramethylimidazolidine Chemical compound CC1CN(C)C(C)N1C KYRYHBRYSSBWLU-UHFFFAOYSA-N 0.000 description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 2
- SMWUDAKKCDQTPV-UHFFFAOYSA-N 1,3-dimethylimidazolidine Chemical compound CN1CCN(C)C1 SMWUDAKKCDQTPV-UHFFFAOYSA-N 0.000 description 2
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 150000005678 chain carbonates Chemical class 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 150000005676 cyclic carbonates Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- GARJMFRQLMUUDD-UHFFFAOYSA-N 1,1-dimethylpyrrolidin-1-ium Chemical compound C[N+]1(C)CCCC1 GARJMFRQLMUUDD-UHFFFAOYSA-N 0.000 description 1
- DNSADNILRQYBAB-UHFFFAOYSA-N 1,2,3,4-tetramethylimidazol-1-ium Chemical compound CC1=C[N+](C)=C(C)N1C DNSADNILRQYBAB-UHFFFAOYSA-N 0.000 description 1
- KCUGPPHNMASOTE-UHFFFAOYSA-N 1,2,3-trimethylimidazol-1-ium Chemical compound CC=1N(C)C=C[N+]=1C KCUGPPHNMASOTE-UHFFFAOYSA-N 0.000 description 1
- QDRFNXRYFUFFLV-UHFFFAOYSA-N 1,2,3-trimethylimidazolidine Chemical compound CC1N(C)CCN1C QDRFNXRYFUFFLV-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
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical class CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- IFGGXMRDYJZDJE-UHFFFAOYSA-N 1,2-dimethyl-3-phenylimidazol-1-ium Chemical compound CN1C=C[N+](C=2C=CC=CC=2)=C1C IFGGXMRDYJZDJE-UHFFFAOYSA-N 0.000 description 1
- UHIFZEQUAVFJKZ-UHFFFAOYSA-N 1,2-dimethyl-3-phenylimidazolidine Chemical compound CC1N(C)CCN1C1=CC=CC=C1 UHIFZEQUAVFJKZ-UHFFFAOYSA-N 0.000 description 1
- CDIWYWUGTVLWJM-UHFFFAOYSA-N 1,3,4-trimethylimidazol-1-ium Chemical compound CC1=C[N+](C)=CN1C CDIWYWUGTVLWJM-UHFFFAOYSA-N 0.000 description 1
- IBXOTQVBNFBJFM-UHFFFAOYSA-N 1,3,4-trimethylimidazolidine Chemical compound CC1CN(C)CN1C IBXOTQVBNFBJFM-UHFFFAOYSA-N 0.000 description 1
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- OBTFKSNFKVPPFY-UHFFFAOYSA-N 1,3-dimethyl-2-phenylimidazol-1-ium Chemical compound CN1C=C[N+](C)=C1C1=CC=CC=C1 OBTFKSNFKVPPFY-UHFFFAOYSA-N 0.000 description 1
- QISTUHYRFABJSG-UHFFFAOYSA-N 1,3-dimethyl-2-phenylimidazolidine Chemical compound CN1CCN(C)C1C1=CC=CC=C1 QISTUHYRFABJSG-UHFFFAOYSA-N 0.000 description 1
- IJDNIXNJORNVTA-UHFFFAOYSA-N 1,3-dimethyl-2-propylimidazol-1-ium Chemical compound CCCC=1N(C)C=C[N+]=1C IJDNIXNJORNVTA-UHFFFAOYSA-N 0.000 description 1
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- HVVRUQBMAZRKPJ-UHFFFAOYSA-N 1,3-dimethylimidazolium Chemical compound CN1C=C[N+](C)=C1 HVVRUQBMAZRKPJ-UHFFFAOYSA-N 0.000 description 1
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- HGIKIBHZIYNEKO-UHFFFAOYSA-N 1-benzyl-2,3-dimethylimidazol-3-ium Chemical compound C1=C[N+](C)=C(C)N1CC1=CC=CC=C1 HGIKIBHZIYNEKO-UHFFFAOYSA-N 0.000 description 1
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- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 235000019253 formic acid Nutrition 0.000 description 1
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 1
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- ZTOMUSMDRMJOTH-UHFFFAOYSA-N glutaronitrile Chemical compound N#CCCCC#N ZTOMUSMDRMJOTH-UHFFFAOYSA-N 0.000 description 1
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- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 description 1
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- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
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- 229910052701 rubidium Inorganic materials 0.000 description 1
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Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Electric Double-Layer Capacitors Or The Like (AREA)
- Secondary Cells (AREA)
Description
そこで、従来より、電解コンデンサ用電解液において、電気伝導率がより高く、熱安定性により優れ、耐電圧性のより高い性質が要求されており、又、これらの性質を兼ね備えることが必要とされていた。
一方、電解コンデンサにおいても、インピーダンスがより低く、熱安定性により優れ、耐電圧性のより高い電解コンデンサが要求されており、又、これらの性質を兼ね備えることが必要とされていた。
しかるに、従来、このような要望に答え得る電解コンデンサ用電解液及び電解コンデンサは実現できていないのが実状である。
本発明の他の目的や新規な特徴については本件明細書及び図面の記載からも明らかになるであろう。
(請求項1)次の一般式(1)で示されるグリコラトオキサラト硼酸イオンを含有する電解コンデンサ用電解液。
(請求項2)グリコラトオキサラト硼酸イオンを、グリコラトオキサラト硼酸イオンの第四級オニウム塩、アミン塩、アンモニウム塩及びアルカリ金属塩からなる群より選択される1種以上の塩の形態で含有する、請求項1に記載の電解コンデンサ用電解液。
(請求項3)第四級オニウム塩が、第四級アンモニウム塩、第四級ホスホニウム塩、第四級イミダゾリウム塩及び第四級アミジニウム塩からなる群より選択される1種以上である、請求項2に記載の電解コンデンサ用電解液。
(請求項4)第四級オニウム塩の炭素数の和が、4〜12である、請求項2又は3に記載の電解コンデンサ用電解液。
(請求項5)溶媒としてγ−ブチロラクトン、炭酸エステル、カルボン酸エステル、リン酸エステル、ニトリル、アミド、スルホン、アルコール、スルホラン及び3−メチルスルホランからなる群より選択される1種以上を含む請求項1〜4いずれか1項に記載の電解コンデンサ用電解液。
(請求項6)請求項1〜5いずれか1項に記載の電解コンデンサ電解液を用いてなる電解コンデンサ。
(請求項7)グリコラトオキサラト硼酸イオンを含有する導電性材料を用いてなる電気化学素子。
更に、電気二重層コンデンサ、イオンの電荷移動による充電/放電機構を有する電池、エレクトロクロミック表示素子などの電気化学素子に使用した場合は、上記のように、インピーダンスが低く、熱安定性に優れ、耐電圧性の高く、電解液と接触する樹脂やゴム、金属を劣化させたり腐食させる等の不具合もないため、信頼性の高い電気化学素子を構成できる。
鎖状炭酸エステル(例えば、炭酸ジメチル、炭酸エチルメチル、炭酸ジエチル、炭酸ジフェニル、炭酸メチルフェニル等の鎖状炭酸エステル)、環状炭酸エステル(例えば、炭酸エチレン、炭酸プロピレン、2,3−ジメチル炭酸エチレン、炭酸ブチレン、炭酸ビニレン、2−ビニル炭酸エチレン等の環状炭酸エステル)等の炭酸エステル;脂肪族カルボン酸エステル(例えば、ギ酸メチル、酢酸メチル、プロピオン酸メチル、酢酸エチル、酢酸プロピル、酢酸ブチル、酢酸アミル等)、芳香族カルボン酸エステル(例えば安息香酸メチル、安息香酸エチル等の芳香族カルボン酸エステル)、ラクトン(例えば、γ−ブチロラクトン、γ−バレロラクトン、δ−バレロラクトン等)等のカルボン酸エステル;リン酸トリメチル、リン酸エチルジメチル、リン酸ジエチルメチル、リン酸トリエチル等のリン酸エステル;アセトニトリル、プロピオニトリル、メトキシプロピオニトリル、グルタロニトリル、アジポニトリル、2−メチルグルタロニトリル等のニトリル;N−メチルホルムアミド、N−エチルホルムアミド、N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミド、N−メチルピロリジノン等のアミド;ジメチルスルホン、エチルメチルスルホン、ジエチルスルホン、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等のスルホン;エチレングリコール、プロピレングリコール、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等のアルコール;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、1,4−ジオキサン、1,3−ジオキソラン、テトラヒドロフラン、2−メチルテトラヒドロフラン、2,6−ジメチルテトラヒドロフラン、テトラヒドロピラン等のエーテル;ジメチルスルホキシド、メチルエチルスルホキシド、ジエチルスルホキシド等のスルホキシド;1,3−ジメチル-2−イミダゾリジノン、1,3−ジメチル−3,4,5,6−テトラヒドロ−2(1H)−ピリミジノン、3−メチル−2−オキサゾリジノンおよびこれら2種以上の混合物が挙げられる。
しかし、従来の電解液及びコンデンサにおいては、これまで定格電圧35V以下の低い電圧領域で使用されていたことから、3重量%程度の水分が存在しても、コンデンサのライフ特性への影響が小さかった。しかし、本発明の電解液を用いたコンデンサは、定格電圧100Vクラスまでの高い電圧領域で使用可能であり、また高耐熱性の要求も満たすものであるため、これまでとは異なり、水分含量の影響が大きい。本発明の電解液は、非水系溶媒を使用した場合、電解液中の水分濃度が、1重量%以下であることが好ましく、上記の化成性をも考慮すれば、好ましくは0.01〜1重量%であり、特に好ましくは0.01〜0.1重量%である。
本発明の電解液は、これに高分子化合物を添加することにより固体化して、いわゆるゲル化電解液として使用してもよい。このようなゲル化電解液に使用される高分子の例としては、ポリエチレンオキシド、ポリアクリロニトリル、ポリテトラフルオロエチレン、ポリフッ化ビニリデン、ポリメチルメタクリレート等を挙げることができる。
本発明の電解液における電解質の含有量は、電解液の総重量に対し通常1〜70重量%、好ましくは5〜40重量%である。この範囲外では電導度が著しく低下する。
電解液のpHは通常3〜11、好ましくは4〜8である。この範囲外では、電解液の火花電圧が低下する。
本発明の電解液において、一般式(1)中のnの値を変化させて30重量%グリコラトオキサラト硼酸トリエチルアミンγ−ブチロラクトン溶液を合成した場合(混合合成)と、比較としてボロジグリコール酸トリエチルアミン塩とボロジシュウ酸トリエチルアミン塩をそのn値に見合うように混合させた場合(分別合成)との場合における電気伝導度の差異を測定した。その結果を、図1に示す。
表1に示す電解液組成の電解液を作成し、当該電解液について、その調製直後及び120℃での加熱試験を500時間実施した後に、それぞれの30℃での電気伝導率(電導度)を測定した。その結果を、表1に示す。
これらの結果を、表2に示す。
更に、電気二重層コンデンサ、イオンの電荷移動による充電/放電機構を有する電池、エレクトロクロミック表示素子などの電気化学素子に使用した場合、インピーダンスが低く、熱安定性に優れ、耐電圧性の高く、電解液と接触する樹脂やゴム、金属を劣化させたり腐食させる等の不具合もないため、信頼性の高い電気化学素子を構成できる。
2 混合合成データ
Claims (7)
- グリコラトオキサラト硼酸イオンを、グリコラトオキサラト硼酸イオンの第四級オニウム塩、アミン塩、アンモニウム塩及びアルカリ金属塩からなる群より選択される1種以上の塩の形態で含有する、請求項1に記載の電解コンデンサ用電解液。
- 第四級オニウム塩が、第四級アンモニウム塩、第四級ホスホニウム塩、第四級イミダゾリウム塩及び第四級アミジニウム塩からなる群より選択される1種以上である、請求項2に記載の電解コンデンサ用電解液。
- 第四級オニウム塩の炭素数の和が、4〜12である、請求項2又は3に記載の電解コンデンサ用電解液。
- 溶媒としてγ−ブチロラクトン、炭酸エステル、カルボン酸エステル、リン酸エステル、ニトリル、アミド、スルホン、アルコール、スルホラン及び3−メチルスルホランからなる群より選択される1種以上を含む請求項1〜4いずれか1項に記載の電解コンデンサ用電解液。
- 請求項1〜5いずれか1項に記載の電解コンデンサ電解液を用いてなる電解コンデンサ。
- グリコラトオキサラト硼酸イオンを含有する導電性材料を用いてなる電気化学素子。
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