JP4125604B2 - 電気二重層コンデンサ - Google Patents
電気二重層コンデンサ Download PDFInfo
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- 239000003990 capacitor Substances 0.000 title claims abstract description 105
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 claims abstract description 24
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000003792 electrolyte Substances 0.000 claims description 25
- 239000011148 porous material Substances 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 239000003575 carbonaceous material Substances 0.000 claims description 7
- 239000011149 active material Substances 0.000 claims description 5
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- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 3
- HUTDDBSSHVOYJR-UHFFFAOYSA-H bis[(2-oxo-1,3,2$l^{5},4$l^{2}-dioxaphosphaplumbetan-2-yl)oxy]lead Chemical compound [Pb+2].[Pb+2].[Pb+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O HUTDDBSSHVOYJR-UHFFFAOYSA-H 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 22
- 239000010410 layer Substances 0.000 description 36
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 14
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- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
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- 229910045601 alloy Inorganic materials 0.000 description 2
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- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- -1 bisulfate ions Chemical class 0.000 description 2
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- 239000007772 electrode material Substances 0.000 description 2
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- 239000012212 insulator Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
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- 230000003197 catalytic effect Effects 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
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- 230000002441 reversible effect Effects 0.000 description 1
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- 238000012546 transfer Methods 0.000 description 1
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Classifications
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- 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
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- 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
-
- 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
- H01G11/04—Hybrid capacitors
-
- 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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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Semiconductor Integrated Circuits (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
Description
電気二重層(EDL)コンデンサの形態を取った蓄電装置は、いくつか存在する。例えば、米国特許第4,313,084号および米国特許第4,562,511号が開示している。このようなコンデンサは、2つの多孔質分極性電極と、両者間に配置した誘電体材料から成る多孔質セパレータと、カレントコレクタとを含む。硫酸水溶液等の非水系または水系の液体電解質は、電極およびセパレータの細孔およびコンデンサケース内の自由空間に保持される。電荷は、電極材料と電解質との間の界面における細孔に蓄積される。分極性電極の製造は、一般に各種多孔質炭素材料が使用される。電気二重層コンデンサの容量を増やすため、これら炭素材料は、あらかじめ活性化され、その比表面積は300〜3000m2/gまで増加する。
本発明の目的は、コンデンサの比エネルギを高め、そのコストを削減することである。
使用した動作条件において、充電状態における上記可逆反応の最大平衡電位は、約1.8Vである。
ここで(H+)ad/eは炭素電極の負荷電表面において電気二重層に吸着したプロトンを示し(コンデンサの充電状態)、(HSO4 −)ad/−eは炭素電極の正荷電表面において電気二重層に吸着した重硫酸塩イオンを示す(コンデンサの放電状態)。発明者等の実験によれば、前記電極の電位は、同一溶液中の通常の水素電極に比べ、−0.2〜1.0Vの範囲で変化した。
ここで注意すべきは、いずれの放電度においても、正電極の活性質量が二酸化鉛と硫酸鉛とを共に含むことである。これは、化学分析の結果、判明した。完全に充電した状態において、PbSO4とPbO2の実際質量比は、一般に約99%PbO2に対する約0.1%PbSO4を下回らない。一方、完全に放電した状態では、一般に約0.1%PbO2に対する約99%PbSO4を上回らない。
実施例1
電気二重層コンデンサ(図1)の構成を説明する。負電極5は8層のTCAタイプ活性炭繊維から成り、比表面積は1200m2/g、各層の厚さは300μmである。正電極7は、1mmの厚さを有し、硫酸鉛と二酸化鉛とを含む固形活物質を有し、94%の鉛と5%のアンチモンとを含む合金から成る格子にプレス成形している。コンデンサはさらに、グレースタイプの多孔質セパレータ6と、ケースの圧力カバー1と、コンデンサ電極間の短絡を防止する絶縁体2と、シート鋼から成るカレントコレクタ3と、黒鉛箔から成るカレントコレクタ保護耐蝕層4と、耐酸性シール材8と、耐圧ケース9とを備える。
実施例1(図1)に説明したコンデンサとは異なる電気二重層コンデンサ(図2)である。これは、2つの負電極を使用する。各負電極は、4層のTCAタイプ活性炭繊維(1200m2/gの比表面と300μmの層厚を有する)から成り、正電極の両側に配置し、相互接続する。正の非分極性電極7は、94%の鉛と5%のアンチモンとを含む合金から成る格子で構成する。83%の固体活物質と17%のポリテトラフルオレチレンから成るペーストを格子の開口に塗布する。化学分析によれば、放電した状態において、組立品の硫酸鉛と二酸化鉛の質量比は、95.8%であった。完全に充電した状態において、その比は5.6%であった。また50%放電においては45.1%であった(これら計算においてPbSO4とPbO2の合計質量を100%とした)。グレースタイプのセパレータ5を使用した。カレントコレクタ3は、シートステンレス鋼で製造した。カレントコレクタ耐蝕保護層4は、0.3mm厚の非多孔質黒鉛ベース炭素材料で形成した。両電極は板状とし、76×74mmの寸法とした。本実施例は、開始密度1.1g/cm2(コンデンサの放電状態において)を有する硫酸電解質を使用した。10kg/cm2の圧縮圧力を電極に適用した。電解質は、電極およびセパレータの細孔内にのみ含めた。細孔体積のうち電解質が無い部分の値は、重量測定によれば、負電極において29%、正電極において19%、セパレータにおいて10.5%であった。
ここでCは静電容量である。電圧におけるこのようなゲインは、比エネルギにおけるゲインを非常に大きくする。
本発明に基づくコンデンサは、国際特許出願WO97/07518に基づく既知の電気二重層コンデンサよりも数倍高い比エネルギを提供し(12.5Wh/lに対して58.9Wh/l)、約10倍低いコストを実現する。本発明に基づくコンデンサは、エレメントの直列および並列接続を可能にし、様々な組合せのコンデンサバッテリの組み立てを可能にする。このコンデンサの重要な利点は、密閉されていることおよびメンテナンスフリーであることである。本コンデンサの性能および特性は、空間位置に左右されない。すなわち、水平、垂直等に配置しても性能および特性は同じである。本発明に基づくコンデンサは、自動車、航空機、宇宙船等におけるように、高い加速度で移動しても通常に機能すると期待される。
Claims (8)
- 炭素材料から成る分極性電極と、二酸化鉛と硫酸鉛とを含む非分極性電極と、前記分極性電極と前記非分極性電極との間のセパレータと、硫酸を含有する水溶液電解質とを備える電気二重層コンデンサであって、
前記硫酸鉛と前記二酸化鉛との質量比は、約0.1〜99%から99〜0.1%の範囲であり、
前記分極性電極は鉛を含有する
コンデンサ。 - 前記分極性電極における鉛の量は、約0.03〜約3重量%の範囲である請求項1記載のコンデンサ。
- 前記非分極性電極は、硫酸鉛質量の約0.2〜約5%の一酸化鉛を含有する請求項1記載のコンデンサ。
- 前記非分極性電極は、当該電極の固体活物質の約0.1〜約5%の燐酸鉛を含有する請求項1記載のコンデンサ。
- 前記分極性電極と前記非分極性電極と前記セパレータと前記水溶液電解質とをケースに収容し、前記分極性電極と前記非分極性電極と前記セパレータとは多孔質であり、前記ケース内における前記電解質の体積は前記電極およびセパレータ中の細孔の合計体積よりも小さい請求項1記載のコンデンサ。
- 前記両電極およびセパレータ中の細孔体積において前記電解質が無い部分の割合は、約10%〜約50%である請求項5記載のコンデンサ。
- 前記ケースは内部空間を有し、当該内部空間は真空である請求項5記載のコンデンサ。
- 前記分極性電極と前記非分極性電極と前記セパレータと前記水溶液電解質とで1つのコンデンサセルを構成し、少なくとも1つのコンデンサセルをケースの圧力カバー間に圧縮収容する請求項1記載のコンデンサ。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/848,724 US6466429B1 (en) | 2001-05-03 | 2001-05-03 | Electric double layer capacitor |
PCT/CA2002/000675 WO2002091412A1 (en) | 2001-05-03 | 2002-05-03 | Electric double layer capacitor |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2004521511A JP2004521511A (ja) | 2004-07-15 |
JP4125604B2 true JP4125604B2 (ja) | 2008-07-30 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2002588580A Expired - Fee Related JP4125604B2 (ja) | 2001-05-03 | 2002-05-03 | 電気二重層コンデンサ |
Country Status (12)
Country | Link |
---|---|
US (1) | US6466429B1 (ja) |
EP (1) | EP1386336B1 (ja) |
JP (1) | JP4125604B2 (ja) |
KR (1) | KR100897945B1 (ja) |
CN (1) | CN100470693C (ja) |
AT (1) | ATE315273T1 (ja) |
AU (1) | AU2002257436B2 (ja) |
CA (1) | CA2446422C (ja) |
DE (1) | DE60208540T2 (ja) |
EA (1) | EA005670B1 (ja) |
HK (1) | HK1063100A1 (ja) |
WO (1) | WO2002091412A1 (ja) |
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EP0247759B1 (en) * | 1986-05-20 | 1993-08-25 | Showa Denko Kabushiki Kaisha | Roll type solid electrolytic capacitor |
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JP4264198B2 (ja) * | 1997-12-18 | 2009-05-13 | ナウチノ−プロイズヴォドストヴェンノエ プレドプリヤーティエ “エクシン” | 二重電気層を備えるコンデンサ |
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EA200301208A1 (ru) | 2004-06-24 |
DE60208540D1 (de) | 2006-03-30 |
EA005670B1 (ru) | 2005-04-28 |
JP2004521511A (ja) | 2004-07-15 |
CA2446422A1 (en) | 2002-11-14 |
CN1518752A (zh) | 2004-08-04 |
AU2002257436B2 (en) | 2006-05-18 |
ATE315273T1 (de) | 2006-02-15 |
KR20040014518A (ko) | 2004-02-14 |
WO2002091412A1 (en) | 2002-11-14 |
DE60208540T2 (de) | 2006-09-21 |
KR100897945B1 (ko) | 2009-05-18 |
CA2446422C (en) | 2009-09-22 |
CN100470693C (zh) | 2009-03-18 |
HK1063100A1 (en) | 2004-12-10 |
EP1386336A1 (en) | 2004-02-04 |
US20020163771A1 (en) | 2002-11-07 |
EP1386336B1 (en) | 2006-01-04 |
US6466429B1 (en) | 2002-10-15 |
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