JP3872182B2 - Electric double layer capacitor - Google Patents
Electric double layer capacitor Download PDFInfo
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- JP3872182B2 JP3872182B2 JP21278797A JP21278797A JP3872182B2 JP 3872182 B2 JP3872182 B2 JP 3872182B2 JP 21278797 A JP21278797 A JP 21278797A JP 21278797 A JP21278797 A JP 21278797A JP 3872182 B2 JP3872182 B2 JP 3872182B2
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- 239000003990 capacitor Substances 0.000 title claims description 46
- 239000003792 electrolyte Substances 0.000 claims description 78
- 239000008151 electrolyte solution Substances 0.000 claims description 47
- 150000003839 salts Chemical class 0.000 claims description 39
- 239000000126 substance Substances 0.000 claims description 38
- 150000001768 cations Chemical class 0.000 claims description 31
- 239000003880 polar aprotic solvent Substances 0.000 claims description 13
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 12
- 150000001450 anions Chemical class 0.000 claims description 6
- 238000007789 sealing Methods 0.000 description 14
- 229940021013 electrolyte solution Drugs 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 4
- -1 hydroxide ions Chemical class 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 229920003026 Acene Polymers 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000000320 amidine group Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- WKFQMDFSDQFAIC-UHFFFAOYSA-N 2,4-dimethylthiolane 1,1-dioxide Chemical compound CC1CC(C)S(=O)(=O)C1 WKFQMDFSDQFAIC-UHFFFAOYSA-N 0.000 description 1
- CMJLMPKFQPJDKP-UHFFFAOYSA-N 3-methylthiolane 1,1-dioxide Chemical compound CC1CCS(=O)(=O)C1 CMJLMPKFQPJDKP-UHFFFAOYSA-N 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 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
- 239000011230 binding agent Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000004010 onium ions Chemical group 0.000 description 1
- 125000005496 phosphonium group Chemical group 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- SZWHXXNVLACKBV-UHFFFAOYSA-N tetraethylphosphanium Chemical compound CC[P+](CC)(CC)CC SZWHXXNVLACKBV-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- SEACXNRNJAXIBM-UHFFFAOYSA-N triethyl(methyl)azanium Chemical compound CC[N+](C)(CC)CC SEACXNRNJAXIBM-UHFFFAOYSA-N 0.000 description 1
- TZWFFXFQARPFJN-UHFFFAOYSA-N triethyl(methyl)phosphanium Chemical compound CC[P+](C)(CC)CC TZWFFXFQARPFJN-UHFFFAOYSA-N 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
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は各種電子機器に利用される電気二重層コンデンサに関するものである。
【０００２】
【従来の技術】
一般にこの種の電気二重層コンデンサは、一対の分極性電極をその間にセパレータを介在させて対向させることによりコンデンサ素子を構成し、そしてこのコンデンサ素子に電解液を含浸させることにより構成している。そして前記分極性電極はアルミニウム箔や銅箔に電極スラリーを所定厚みに塗布したものであって、電極スラリーは活性炭、グラファイトもしくはポリアセン系有機半導体とカーボンブラック、アセチレンブラックもしくはケッチェンブラックを混合したものにバインダーとしてＰＴＦＥやＣＭＣなどを加え、純水やアルコールで湿潤させたものである。
【０００３】
電解液の溶媒としては、プロピレンカーボネート、γ−ブチロラクトン、エチレンカーボネート、スルホラン、アセトニトリル、ジメチルカーボネート、ジエチルカーボネートまたはメチルエチルカーボネートのいずれか１種もしくは２種以上の混合物が用いられている。また、電解質カチオンとしては、第四級アンモニウムもしくは第四級ホスホニウムが使用され、一方、電解質アニオンとしては、ＢＦ4 -，ＰＦ6 -，ＣｌＯ4 -，ＣＦ3ＳＯ3 -またはＮ（ＣＦ3ＳＯ2)2 -が用いられている。
【０００４】
また、電解液の溶媒にスルホランまたはその誘導体を用いると耐電圧の高い電気二重層コンデンサが得られることが知られている（特開昭６２−２３７７１５号公報参照）。そしてまた電解質にＮ，Ｎ，Ｎ′−置換アミジン基を有する化合物の第四級塩を用いることにより封口体の封口性能を低下させる水酸化物イオンの生成を抑制できることが知られている。
【０００５】
【発明が解決しようとする課題】
しかしながら、上記した従来の電気二重層コンデンサでは、非水系電解液の電解質として第四級アンモニウム塩もしくは第四級ホスホニウム塩が使用されているため、この非水系の電解液を用いて電気二重層コンデンサを作製した場合、６０℃での耐圧はほぼ２．３Ｖ〜２．５Ｖであり、この場合、これ以上の電圧を印加すると容量、内部抵抗や外観寸法の変化が大きくなるという問題点を有していた。
【０００６】
また、特開昭６２−２３７７１５号公報に記載された電解液の溶媒であるスルホランはプロピレンカーボネートなどの従来の電解液に用いられる溶媒に比べて電解質の溶解度が低いため、電解液の電気伝導度が低く、そのため、電気二重層コンデンサの内部抵抗が上昇する。さらにスルホランはプロピレンカーボネートなどの従来の電解液に用いられる溶媒に比べて融点が高いことから、スルホラン溶媒の電解液を用いた電気二重層コンデンサは低温での特性に問題点を有していた。
【０００７】
また、Ｎ，Ｎ，Ｎ′−置換アミジン基を有する化合物の第四級塩を電気二重層コンデンサ用電解液の電解質として使用した場合、電解質カチオン成分自体が分極性電極の表面で電気化学反応を起こすものもあり、これにより、電気二重層コンデンサの内部抵抗変化や容量変化が大きくなる等の問題点を有していた。
【０００８】
本発明は上記従来の問題点を解決するもので、非水系電解液の電気伝導度、耐電圧および耐熱性を向上させることができるとともに、陰極側分極性電極の表面もしくは陰極側分極性電極に接続された引き出しリードの表面で発生する強アルカリ成分を消失させることができ、これにより、内部抵抗が低く、かつ耐電圧ならびに耐熱性が高く、しかも封口体の封口性能が低下することもない電気二重層コンデンサを提供することを目的とするものである。
【０００９】
【課題を解決するための手段】
上記目的を達成するために本発明の電気二重層コンデンサは、分極性電極と、この分極性電極に含浸される非水系電解液とを有し、前記非水系電解液が極性非プロトン溶媒と、電解質として第四級オニウム塩と（化６）または（化７）で示される電解質カチオン成分およびＢＦ 4 - の電解質アニオンを有する塩の混合系電解質で構成したもので、この構成によれば、非水系電解液の電気伝導度、耐電圧および耐熱性を向上させることができるとともに、陰極側分極性電極の表面もしくは陰極側分極性電極に接続された引き出しリードの表面で発生する強アルカリ成分を消失させることができ、これにより、内部抵抗が低く、かつ耐電圧ならびに耐熱性が高く、しかも封口体の封口性能が低下することもない電気二重層コンデンサを得ることができるものである。
【００１０】
【化６】
【化７】
【発明の実施の形態】
本発明の請求項１に記載の発明は、分極性電極と、この分極性電極に含浸される非水系電解液とを有し、前記非水系電解液が極性非プロトン溶媒と、電解質として第四級オニウム塩と（化６）または（化７）で示される電解質カチオン成分およびＢＦ 4 - の電解質アニオンを有する塩の混合系電解質で構成したもので、この構成によれば、電解質カチオン成分（化６）または（化７）が第四級オニウム塩に比べ、極性溶媒中での移動度が大きいと考えられることから当量電気伝導度が高く、また電解質カチオン成分（化６）または（化７）を用いた電解液は第四級オニウム塩を用いた電解液より電気化学的に安定な電位領域（電位窓）が広いため、高い耐電圧を示すとともに、電解質を混合することにより電解質の溶解性が向上するもので、これにより、内部抵抗が低く高耐電圧で低温での安定性が高い電気二重層コンデンサが得られるものである。
【００１３】
また、混合系電解質の電解質カチオン成分（化６）または（化７）は、陰極側分極性電極の表面もしくは陰極側分極性電極に接続された引き出しリードの表面で発生する強アルカリ成分である水酸化物イオンを消失させるため、強アルカリ成分による封口体の封口性能の低下ということもなく、これにより、アルカリ性電解液の漏出を確実に防ぐことができるものである。
【００１４】
請求項２に記載の発明は、非水系電解液における混合系電解質の混合比率を第四級オニウム塩の重量１に対し、（化６）または（化７）で示される電解質カチオン成分を有する塩の重量を０．１以上としたもので、この構成においては、第四級オニウム塩と（化６）または（化７）で示される電解質カチオン成分を有する塩が広い温度範囲で極性溶媒に安定に溶解し、高い電気伝導度を示すと同時に広い電位窓を示すことにより、広い温度範囲で内部抵抗が低くかつ高耐電圧の電気二重層コンデンサを得ることができるものである。
【００１５】
また、第四級オニウム塩の重量１に対し、（化６）または（化７）で示される電解質カチオン成分を有する塩の重量が０．１より小さい場合は、電解液の電気伝導度上昇の効果や耐電圧上昇の効果が見られなくなり、電気二重層コンデンサの内部抵抗低減、耐電圧向上の効果が得られなくなるとともに低温での容量変化が大きくなる問題点があり、したがって、（化６）または（化７）で示される電解質カチオン成分を有する塩の重量は第四級オニウム塩の重量１に対し０．１以上が最適である。
【００１６】
請求項３に記載の発明は、混合系電解質の濃度を３．０モル／ｋｇ以下としたもので、この構成においては、混合系電解質が広い温度範囲で安定に極性溶媒に溶解しているため、この混合系電解質を用いた電気二重層コンデンサは広い温度範囲で内部抵抗が低くかつ高耐電圧の効果が得られるものである。
【００１７】
また、混合系電解質の濃度が３．０モル／ｋｇ以上の場合は低温で電解質が析出し、安定性が低下するなどの不具合を起こすおそれがあり、したがって、混合系電解質の濃度は３．０モル／ｋｇ以下が最適である。
【００１８】
請求項４に記載の発明は、非水系電解液の含まれる水分を３０００ｐｐｍ以下としたもので、この構成においては、非水系電解液の水分による電位窓の変化が比較的小さいため、電気二重層コンデンサ用電解液としての耐電圧を十分有していると考えられるが、非水系電解液の含水率が３０００ｐｐｍを超える場合は、電解液中の水分の電気分解により電解液の耐電圧が低下し、請求項１〜３のいずれか１つに記載の構成で得られる耐電圧上昇の効果が得られなくなるものであり、したがって、非水系電解液の含水率は３０００ｐｐｍ以下が適正であると考えられる。
【００１９】
請求項５に記載の発明は、（化６）で示される電解質カチオン成分が（化８）であり、この電解質カチオン成分を有する塩と第四級オニウム塩の混合系電解質を極性非プロトン溶媒に溶解してなる混合系電解液を用いたもので、この構成によれば、（化８）で示される電解質カチオン成分の塩が電気化学的に安定なことと極性非プロトン溶媒への溶解度が高いため、耐電圧が高くかつ低温での安定性が高い電気二重層コンデンサが得られるものである。
【００２０】
【化８】
請求項６に記載の発明は、（化６）で示される電解質カチオン成分が（化９）であり、この電解質カチオン成分を有する塩と第四級オニウム塩の混合系電解質を極性非プロトン溶媒に溶解してなる混合系電解液を用いたもので、この構成によれば、（化９）で示される電解質カチオン成分の塩が電気化学的に安定であり高い耐電圧を示すとともに、極性非プロトン溶媒中での移動度が高いため、この電解質カチオン成分の塩を用いた電解液は高い電気伝導度を示すものであり、これらの構成により、耐電圧が高くかつ内部抵抗が低い電気二重層コンデンサが得られるものである。
【００２２】
【化９】
請求項７に記載の発明は、（化６）で示される電解質カチオン成分が（化１０）であり、この電解質カチオン成分を有する塩と第四級オニウム塩の混合系電解質を極性非プロトン溶媒に溶解してなる混合系電解液を用いたもので、電気二重層コンデンサであり、この構成によれば、（化１０）で示される電解質カチオン成分の塩が電気化学的に安定であり高い耐電圧を示すとともに、高い耐熱性を示すものであり、これらの構成により、耐電圧が高くかつ高い耐熱性を有する電気二重層コンデンサが得られるものである。
【００２４】
【化１０】
以下、本発明の一実施の形態について説明する。
本発明の電気二重層コンデンサの基本は、分極性電極と、この分極性電極に含浸される非水系電解液とを有し、前記非水系電解液が極性非プロトン溶媒と、電解質として第四級オニウム塩と（化６）または（化７）で示される電解質カチオン成分およびＢＦ 4 - の電解質アニオンを有する塩の混合系電解質で構成したものである。
【００２６】
本発明に用いられる極性非プロトン溶媒としては、プロピレンカーボネート、エチレンカーボネート、ブチレンカーボネート、γ−ブチロラクトン、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、アセトニトリルのいずれか１種もしくは２種以上の混合物が挙げられる。
【００２７】
本発明に用いられる第四級オニウムイオンとして、テトラエチルアンモニウム、メチルトリエチルアンモニウム、テトラエチルホスホニウム、メチルトリエチルホスホニウム、テトラブチルアンモニウム、テトラブチルホスホニウム等が挙げられる。
【００２９】
本発明の電解液には必要により副溶媒を含有させることもできる。副溶媒としては、テトラヒドロフラン、ジメチルカーボネート、ジエチルカーボネート、メチルエチルカーボネート等が挙げられる。
【００３０】
本発明の電解液での電解質の濃度が３．０モル／ｋｇ以上の場合は飽和溶解度を超えて低温で溶媒中に電解質が析出してくるものであり、したがって、電解質の濃度は３．０モル／ｋｇ以下が好適であり、高い電導性や広い温度範囲で電解液の安定性を得るためには、特に０．５〜２．０モル／ｋｇの範囲が好ましい。
【００３１】
本発明で使用する分極性電極は活性炭、グラファイト、ポリアセン系有機半導体のいずれか１種もしくは２種以上の混合物で構成した炭素材料を含有するものである。
【００３２】
本発明の非水系電解液に含まれる水分は３０００ｐｐｍ以下である。
（表１）は本発明の実施の形態１〜５および従来例１〜３の電解液組成を示したものである。（表２）は本発明の実施の形態１〜５および従来例１〜３の電解液について電解質濃度と、温度３０℃で電気伝導度を測定した結果および捲回形の電気二重層コンデンサ（定格電圧２．５Ｖ−静電容量３０Ｆ、サイズ；φ１８ｍｍ×Ｌ４０ｍｍ）を作製したときの内部抵抗を示したものである。
【００３３】
【表１】
【表２】
（表２）から明らかなように、本発明の実施の形態１〜５の電解液は従来例１〜３の電解液と比較して高い電気伝導度を示し、これにより、内部抵抗の低い電気二重層コンデンサが得られることがわかる。
【００３６】
次に本発明の実施の形態１および従来例１の電解液を使用して、サイクリックボルタンメトリーによる各電解液の電位窓の測定を行った。本発明の実施の形態１の測定結果を図１に示し、従来例１の測定結果を図２に示す。また、サイクリックボルタンメトリーの測定条件を（表３）に示す。
【００３７】
【表３】
図１と図２の比較から明らかなように、本発明の実施の形態１の電解液は従来例１の電解液に比べて電位窓が広く、高い耐電圧を有していることがわかる。
【００３９】
次に、本発明の実施の形態１〜５および従来例１〜３の電解液を使用して捲回形の電気二重層コンデンサ（定格電圧２．５Ｖ−静電容量１０Ｆ、サイズ；φ１８ｍｍ×Ｌ３５ｍｍ）を作製した。そしてこれらの電気二重層コンデンサに６０℃で３．０Ｖの電圧を印加したときの２０００時間後の容量変化率を測定した。その測定結果を（表４）に示す。
【００４０】
【表４】
（表４）から明らかなように、本発明の実施の形態１〜５の電解液を使用した電気二重層コンデンサは、従来例１〜３の電解液を使用した電気二重層コンデンサに比べて容量変化率が小さく、高耐電圧の電気二重層コンデンサを構成することができるものである。
【００４２】
次に、上記した本発明の実施の形態１〜５および従来例１〜３の電解液を使用した捲回形の電気二重層コンデンサに７０℃で３．０Ｖの電圧を印加したときの２０００時間後の信頼性評価を実施し、その試験終了後に電気二重層コンデンサの封口体を構成する封口ゴム面の状態を観察した。その観察結果を（表５）に示す。
【００４３】
【表５】
（表５）から明らかなように、本発明の実施の形態１〜５の電解液を用いた電気二重層コンデンサは、電解液中に封口体の封口性能低下につながる過剰の水酸化イオンを消失させることができる（化６）または（化７）で示される電解液カチオン成分を含んでいるため、封口体を劣化させることもなく高信頼性の電気二重層コンデンサを構成することができるものである。
【００４５】
なお、上記本発明の実施の形態１〜５においては捲回形電気二重層コンデンサについて説明したが、コイン形や積層形など他の構造の電気二重層コンデンサの電解液に適用しても、本発明の実施の形態１〜５と同様の効果が得られるものである。
【００４６】
【発明の効果】
以上のように本発明の電気二重層コンデンサは、分極性電極と、この分極性電極に含浸される非水系電解液とを有し、前記非水系電解液が極性非プロトン溶媒と、電解質として第四級オニウム塩と（化６）または（化７）で示される電解質カチオン成分およびＢＦ 4 - の電解質アニオンを有する塩の混合系電解質で構成したもので、この構成によれば、非水系電解液の電気伝導度、耐電圧および耐熱性を向上させることができ、しかも陰極側分極性電極の表面もしくは陰極側分極性電極に接続された引き出しリードの表面で発生する強アルカリ成分である水酸化物イオンも消失させることができるため、内部抵抗が低く、耐電圧、耐熱性が高く、さらには強アルカリ成分による封口体の封口性能の低下も防ぐことができる電気二重層コンデンサが得られるものである。
【図面の簡単な説明】
【図１】本発明の実施の形態１の電解液を使用したサイクリックボルタンメトリーによる電解液の電位窓の測定結果を示す特性図
【図２】従来例１の電解液を使用したサイクリックボルタンメトリーによる電解液の電位窓の測定結果を示す特性図[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an electric double layer capacitor used in various electronic devices.
[0002]
[Prior art]
In general, this type of electric double layer capacitor is configured by forming a capacitor element by facing a pair of polarizable electrodes with a separator interposed therebetween, and impregnating the capacitor element with an electrolytic solution. The polarizable electrode is obtained by applying an electrode slurry to aluminum foil or copper foil to a predetermined thickness, and the electrode slurry is a mixture of activated carbon, graphite or polyacene organic semiconductor and carbon black, acetylene black or ketjen black. PTFE, CMC or the like is added as a binder, and it is wetted with pure water or alcohol.
[0003]
As the solvent for the electrolytic solution, propylene carbonate, γ-butyrolactone, ethylene carbonate, sulfolane, acetonitrile, dimethyl carbonate, diethyl carbonate, or methyl ethyl carbonate is used, or a mixture of two or more thereof. Further, quaternary ammonium or quaternary phosphonium is used as the electrolyte cation, while BF 4 − , PF 6 − , ClO 4 − , CF 3 SO 3 − or N (CF 3 SO 3) is used as the electrolyte anion. 2 ) 2 - is used.
[0004]
In addition, it is known that an electric double layer capacitor having a high withstand voltage can be obtained when sulfolane or a derivative thereof is used as a solvent of an electrolytic solution (see Japanese Patent Application Laid-Open No. 62-237715). It is also known that the use of a quaternary salt of a compound having an N, N, N′-substituted amidine group in the electrolyte can suppress the production of hydroxide ions that degrade the sealing performance of the sealing body.
[0005]
[Problems to be solved by the invention]
However, in the conventional electric double layer capacitor described above, a quaternary ammonium salt or a quaternary phosphonium salt is used as the electrolyte of the non-aqueous electrolyte solution. The breakdown voltage at 60 ° C. is approximately 2.3 V to 2.5 V. In this case, when a voltage higher than this is applied, there is a problem that the change in capacity, internal resistance, and external dimensions increases. It was.
[0006]
In addition, since sulfolane, which is a solvent of an electrolytic solution described in JP-A-62-237715, has lower electrolyte solubility than a solvent used in a conventional electrolytic solution such as propylene carbonate, the electrical conductivity of the electrolytic solution. Therefore, the internal resistance of the electric double layer capacitor increases. Furthermore, since sulfolane has a higher melting point than solvents used in conventional electrolytes such as propylene carbonate, electric double layer capacitors using sulfolane solvent electrolytes have problems with low-temperature characteristics.
[0007]
In addition, when a quaternary salt of a compound having an N, N, N′-substituted amidine group is used as an electrolyte of an electrolytic solution for an electric double layer capacitor, the electrolyte cation component itself undergoes an electrochemical reaction on the surface of the polarizable electrode. In some cases, this causes problems such as a large internal resistance change and capacitance change of the electric double layer capacitor.
[0008]
The present invention solves the above-mentioned conventional problems, and can improve the electrical conductivity, withstand voltage and heat resistance of the non-aqueous electrolyte, and can be applied to the surface of the cathode side polarizable electrode or the cathode side polarizable electrode. The strong alkali component generated on the surface of the connected lead leads can be eliminated, which makes the internal resistance low, withstand voltage and heat resistance high, and does not reduce the sealing performance of the sealing body. An object of the present invention is to provide a double layer capacitor.
[0009]
[Means for Solving the Problems]
In order to achieve the above object, the electric double layer capacitor of the present invention has a polarizable electrode and a nonaqueous electrolyte solution impregnated in the polarizable electrode, and the nonaqueous electrolyte solution is a polar aprotic solvent, quaternary onium salt and (Formula 6) or (Formula 7) electrolytic cation component and BF 4 represented by as an electrolyte - which was composed of a mixture based electrolyte salt with the electrolyte anions, according to this structure, a The electrical conductivity, withstand voltage and heat resistance of the aqueous electrolyte can be improved, and strong alkali components generated on the surface of the cathode-side polarizable electrode or on the surface of the lead lead connected to the cathode-side polarizable electrode are eliminated. As a result, it is possible to obtain an electric double layer capacitor that has low internal resistance, high withstand voltage and heat resistance, and that does not deteriorate the sealing performance of the sealing body. It is possible.
[0010]
[Chemical 6]
[Chemical 7]
DETAILED DESCRIPTION OF THE INVENTION
According to a first aspect of the present invention, a polarizable electrode, and a nonaqueous electrolytic solution is impregnated into the polarizable electrode, the a non-aqueous electrolyte is a polar aprotic solvent, fourth as the electrolyte This is composed of a mixed electrolyte of a salt having a cation salt of the grade onium salt and an electrolyte cation component represented by (Chemical Formula 6) or (Chemical Formula 7) and a BF 4 − electrolyte anion . 6) or (Chemical formula 7) is considered to have a higher mobility in a polar solvent than a quaternary onium salt, so that the equivalent electrical conductivity is high, and the electrolyte cation component (Chemical formula 6) or (Chemical formula 7) Electrolyte solution with a broader electrochemically stable potential region (potential window) than electrolyte solution with quaternary onium salt shows high withstand voltage and solubility of electrolyte by mixing electrolyte This will improve As a result, an electric double layer capacitor having low internal resistance, high withstand voltage, and high stability at low temperatures can be obtained.
[0013]
The electrolyte cation component (Chem. 6) or (Chem. 7) of the mixed electrolyte is water that is a strong alkali component generated on the surface of the cathode-side polarizable electrode or the surface of the lead lead connected to the cathode-side polarizable electrode. Since the oxide ions are eliminated, the sealing performance of the sealing body due to the strong alkali component is not deteriorated, and thereby leakage of the alkaline electrolyte can be surely prevented.
[0014]
The invention according to
[0015]
In addition, when the weight of the salt having an electrolyte cation component represented by (Chemical Formula 6) or (Chemical Formula 7) is less than 0.1 with respect to the weight of the quaternary onium salt, the electrical conductivity of the electrolytic solution is increased. There is a problem that the effect of increasing the withstand voltage and the effect of increasing the withstand voltage are not seen, the effect of reducing the internal resistance of the electric double layer capacitor and improving the withstand voltage cannot be obtained, and the capacitance change at low temperature becomes large. Or, the weight of the salt having the electrolyte cation component represented by (Chemical Formula 7) is optimally 0.1 or more with respect to the weight 1 of the quaternary onium salt.
[0016]
In the invention according to
[0017]
In addition, when the concentration of the mixed electrolyte is 3.0 mol / kg or more, the electrolyte may be deposited at a low temperature, which may cause problems such as a decrease in stability. Therefore, the concentration of the mixed electrolyte is 3.0. Mole / kg or less is optimal.
[0018]
In the invention according to claim 4, the moisture contained in the non-aqueous electrolyte is 3000 ppm or less, and in this configuration, the change in the potential window due to the moisture of the non-aqueous electrolyte is relatively small. Although it is considered that the withstand voltage of the electrolytic solution for capacitors is sufficient, when the water content of the nonaqueous electrolytic solution exceeds 3000 ppm, the withstand voltage of the electrolytic solution decreases due to the electrolysis of water in the electrolytic solution. Thus, the effect of increasing the withstand voltage obtained with the configuration according to any one of claims 1 to 3 cannot be obtained, and therefore, the water content of the non-aqueous electrolyte solution is considered to be 3000 ppm or less. .
[0019]
In the invention according to claim 5, the electrolyte cation component represented by (Chemical Formula 6) is (Chemical Formula 8), and a mixed electrolyte of a salt having the electrolyte cation component and a quaternary onium salt is used as a polar aprotic solvent. This is a mixed electrolytic solution that is dissolved. According to this configuration, the salt of the electrolyte cation component represented by (Chemical Formula 8) is electrochemically stable and has high solubility in a polar aprotic solvent. Therefore, an electric double layer capacitor having a high withstand voltage and high stability at a low temperature can be obtained.
[0020]
[Chemical 8]
In the invention of claim 6, the electrolyte cation component represented by (Chemical Formula 6) is (Chemical Formula 9), and a mixed electrolyte of a salt having the electrolyte cation component and a quaternary onium salt is used as a polar aprotic solvent. According to this configuration, a salt of the electrolyte cation component represented by (Chemical Formula 9) is electrochemically stable and has a high withstand voltage, and is also polar aprotic. Because of its high mobility in the solvent, the electrolytic solution using the salt of the electrolyte cation component exhibits high electrical conductivity. With these configurations, an electric double layer capacitor having high withstand voltage and low internal resistance Is obtained.
[0022]
[Chemical 9]
In the invention according to claim 7, the electrolyte cation component represented by (Chemical Formula 6) is (Chemical Formula 10), and a mixed electrolyte of a salt having the electrolyte cation component and a quaternary onium salt is used as a polar aprotic solvent. This is an electric double layer capacitor that uses a mixed electrolyte solution that is dissolved. According to this configuration, the salt of the electrolyte cation component represented by (Chemical Formula 10) is electrochemically stable and has a high withstand voltage. In addition, the electric double layer capacitor having high withstand voltage and high heat resistance can be obtained.
[0024]
[Chemical Formula 10]
Hereinafter, an embodiment of the present invention will be described.
The basic of the electric double layer capacitor of the present invention includes a polarizable electrode and a nonaqueous electrolytic solution impregnated in the polarizable electrode, the nonaqueous electrolytic solution being a polar aprotic solvent and a quaternary as an electrolyte. It is composed of a mixed electrolyte of an onium salt and a salt having an electrolyte cation component represented by (Chemical Formula 6) or (Chemical Formula 7) and an electrolyte anion of BF 4 − .
[0026]
As the polar aprotic solvent used in the present invention, one or more of propylene carbonate, ethylene carbonate, butylene carbonate, γ-butyrolactone, sulfolane, 3-methylsulfolane, 2,4-dimethylsulfolane, and acetonitrile are used. A mixture is mentioned.
[0027]
Examples of the quaternary onium ion used in the present invention include tetraethylammonium, methyltriethylammonium, tetraethylphosphonium, methyltriethylphosphonium, tetrabutylammonium, tetrabutylphosphonium and the like.
[0029]
If necessary, the electrolytic solution of the present invention may contain a secondary solvent. Examples of the auxiliary solvent include tetrahydrofuran, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, and the like.
[0030]
When the concentration of the electrolyte in the electrolytic solution of the present invention is 3.0 mol / kg or more, the electrolyte is deposited in the solvent at a low temperature exceeding the saturation solubility. Therefore, the concentration of the electrolyte is 3.0. The mol / kg or less is suitable, and in order to obtain high conductivity and stability of the electrolytic solution in a wide temperature range, the range of 0.5 to 2.0 mol / kg is particularly preferable.
[0031]
The polarizable electrode used in the present invention contains a carbon material composed of activated carbon, graphite, or a mixture of two or more of polyacene organic semiconductors.
[0032]
The moisture contained in the non-aqueous electrolyte of the present invention is 3000 ppm or less.
(Table 1) shows the electrolyte compositions of Embodiments 1 to 5 of the present invention and Conventional Examples 1 to 3. (Table 2) shows the results of measuring the electrolyte concentration and the electric conductivity at a temperature of 30 ° C. for the electrolytic solutions of Embodiments 1 to 5 of the present invention and Conventional Examples 1 to 3, and a wound electric double layer capacitor (rated This shows the internal resistance when a voltage of 2.5 V-capacitance of 30 F, size: φ18 mm × L40 mm) is produced.
[0033]
[Table 1]
[Table 2]
As is clear from Table 2, the electrolytic solutions of Embodiments 1 to 5 of the present invention exhibit higher electrical conductivity than the electrolytic solutions of Conventional Examples 1 to 3, and thus have an electric resistance with a low internal resistance. It can be seen that a double layer capacitor is obtained.
[0036]
Next, the potential window of each electrolyte solution was measured by cyclic voltammetry using the electrolyte solutions of Embodiment 1 and Conventional Example 1 of the present invention. The measurement result of Embodiment 1 of the present invention is shown in FIG. 1, and the measurement result of Conventional Example 1 is shown in FIG. Moreover, the measurement conditions of cyclic voltammetry are shown in (Table 3).
[0037]
[Table 3]
As is apparent from the comparison between FIG. 1 and FIG. 2, it can be seen that the electrolytic solution of Embodiment 1 of the present invention has a wider potential window and a higher withstand voltage than the electrolytic solution of Conventional Example 1.
[0039]
Next, a wound-type electric double layer capacitor (rated voltage 2.5 V-capacitance 10 F, size: φ18 mm × L35 mm) using the electrolytes of Embodiments 1 to 5 of the present invention and Conventional Examples 1 to 3 ) Was produced. The capacity change rate after 2000 hours when a voltage of 3.0 V was applied to these electric double layer capacitors at 60 ° C. was measured. The measurement results are shown in (Table 4).
[0040]
[Table 4]
As apparent from (Table 4), the electric double layer capacitor using the electrolytic solution of Embodiments 1 to 5 of the present invention has a capacity compared to the electric double layer capacitor using the electrolytic solution of Conventional Examples 1 to 3. An electric double layer capacitor having a small change rate and a high withstand voltage can be configured.
[0042]
Next, 2000 hours when a voltage of 3.0 V is applied at 70 ° C. to the wound electric double layer capacitor using the electrolytic solutions of Embodiments 1 to 5 and Conventional Examples 1 to 3 described above. Later, the reliability was evaluated, and after the test, the state of the sealing rubber surface constituting the sealing body of the electric double layer capacitor was observed. The observation results are shown in (Table 5).
[0043]
[Table 5]
As is clear from (Table 5), the electric double layer capacitor using the electrolytic solution according to the first to fifth embodiments of the present invention loses excess hydroxide ions that lead to deterioration of the sealing performance of the sealing body in the electrolytic solution. Since the electrolytic solution cation component represented by (Chemical Formula 6) or (Chemical Formula 7) can be included, a highly reliable electric double layer capacitor can be configured without deteriorating the sealing body. is there.
[0045]
In addition, in Embodiments 1 to 5 of the present invention described above, the wound type electric double layer capacitor has been described, but the present invention can be applied to an electrolytic solution of an electric double layer capacitor having another structure such as a coin type or a laminated type. The same effects as those of the first to fifth embodiments of the invention can be obtained.
[0046]
【The invention's effect】
The electric double layer capacitor of the present invention as described above, the polarizable electrode, and a nonaqueous electrolytic solution is impregnated into the polarizable electrode, the non-aqueous electrolyte solution is a polar aprotic solvent, first as an electrolyte It is composed of a mixed electrolyte of a quaternary onium salt and a salt having an electrolyte cation component represented by (Chem. 6) or (Chem. 7) and a BF 4 − electrolyte anion. Hydroxide, which is a strong alkali component that can be improved on the surface of the cathode-side polarizable electrode or the surface of the lead lead connected to the cathode-side polarizable electrode. Electric double layer capacitor with low internal resistance, high withstand voltage, high heat resistance, and prevention of deterioration of sealing performance due to strong alkali components because ions can be eliminated Is obtained.
[Brief description of the drawings]
FIG. 1 is a characteristic diagram showing a measurement result of a potential window of an electrolytic solution by cyclic voltammetry using the electrolytic solution of Embodiment 1 of the present invention. FIG. 2 is a cyclic voltammetry using an electrolytic solution of Conventional Example 1. Characteristic diagram showing measurement results of potential window of electrolyte
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21278797A JP3872182B2 (en) | 1997-08-07 | 1997-08-07 | Electric double layer capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21278797A JP3872182B2 (en) | 1997-08-07 | 1997-08-07 | Electric double layer capacitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1154376A JPH1154376A (en) | 1999-02-26 |
| JP3872182B2 true JP3872182B2 (en) | 2007-01-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21278797A Expired - Fee Related JP3872182B2 (en) | 1997-08-07 | 1997-08-07 | Electric double layer capacitor |
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| JP (1) | JP3872182B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004140293A (en) * | 2002-10-21 | 2004-05-13 | Honda Motor Co Ltd | Nonaqueous electrolyte for electric double-layer capacitor, and electric double-layer capacitor using it |
| WO2004109727A1 (en) * | 2003-06-09 | 2004-12-16 | Matsushita Electric Industrial Co., Ltd. | Electrolytic solution for electrochemical element, method of searching for the same, method of producing the same, and electrochemical element |
| EP1876611A4 (en) * | 2005-04-12 | 2009-12-09 | Sumitomo Chemical Co | Electric double layer capacitor |
| US7800886B2 (en) | 2005-04-12 | 2010-09-21 | Sumitomo Chemical Company, Limited | Electric double layer capacitor |
| JP4894282B2 (en) | 2005-08-26 | 2012-03-14 | パナソニック株式会社 | Electric double layer capacitor |
| EP2785726B1 (en) | 2011-12-02 | 2018-08-01 | Dow Silicones Corporation | Ester-functional silanes and the preparation and use thereof; and use of iminium compounds as phase transfer catalysts |
| CN108172900B (en) * | 2017-12-18 | 2019-08-16 | 中节能万润股份有限公司 | A kind of new lithium salts and its preparation method and application |
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1997
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