JP2007508709A - エネルギー貯蔵装置のための電極および該電極に基づいた電気化学スーパーコンデンサー - Google Patents
エネルギー貯蔵装置のための電極および該電極に基づいた電気化学スーパーコンデンサー Download PDFInfo
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- 238000004146 energy storage Methods 0.000 title claims description 21
- 229920000642 polymer Polymers 0.000 claims abstract description 66
- 239000003990 capacitor Substances 0.000 claims abstract description 32
- 239000002262 Schiff base Substances 0.000 claims abstract description 26
- 150000004753 Schiff bases Chemical class 0.000 claims abstract description 26
- 239000003792 electrolyte Substances 0.000 claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 18
- 125000001424 substituent group Chemical group 0.000 claims abstract description 17
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 15
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 15
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 15
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 13
- 150000003624 transition metals Chemical class 0.000 claims abstract description 13
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 12
- 125000000524 functional group Chemical group 0.000 claims abstract description 9
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 8
- 150000002367 halogens Chemical class 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract 3
- 239000001257 hydrogen Substances 0.000 claims abstract 3
- 150000001875 compounds Chemical class 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 16
- 229910052744 lithium Inorganic materials 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 claims description 11
- -1 alkali metal salt Chemical class 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- HLZSFYMNDQDMLG-UHFFFAOYSA-N 2-hydroxybenzaldehyde;n,n,n',n'-tetramethylethane-1,2-diamine Chemical compound CN(C)CCN(C)C.OC1=CC=CC=C1C=O.OC1=CC=CC=C1C=O HLZSFYMNDQDMLG-UHFFFAOYSA-N 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 239000011149 active material Substances 0.000 claims description 2
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- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000006260 foam Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 239000002562 thickening agent Substances 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical group OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 description 17
- 230000008569 process Effects 0.000 description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 10
- 239000010410 layer Substances 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
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- 238000006722 reduction reaction Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- PWRSNLQOHLSQCA-UHFFFAOYSA-N benzene-1,2-diamine;2-hydroxybenzaldehyde Chemical compound NC1=CC=CC=C1N.OC1=CC=CC=C1C=O.OC1=CC=CC=C1C=O PWRSNLQOHLSQCA-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
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- 230000008859 change Effects 0.000 description 3
- 238000012983 electrochemical energy storage Methods 0.000 description 3
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- 239000003446 ligand Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
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- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LZOZLBFZGFLFBV-UHFFFAOYSA-N sulfene Chemical group C=S(=O)=O LZOZLBFZGFLFBV-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- ZYDVNTYVDVZMKF-UHFFFAOYSA-N [Cl].[Ag] Chemical compound [Cl].[Ag] ZYDVNTYVDVZMKF-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004870 electrical engineering Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000011245 gel electrolyte Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- 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
- H01G11/02—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 using combined reduction-oxidation reactions, e.g. redox arrangement or solion
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- H—ELECTRICITY
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- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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Abstract
Description
電流の二次ソースによって、電力を外部電気回路に蓄積、保存そして放出することが可能である。これらの二次ソースには、慣用電池、慣用コンデンサーおよび電気化学コンデンサー(スーパーコンデンサーまたはウルトラコンデンサーとも呼ばれる)がある。
(ここで、Meは遷移金属であり;
サレンはシッフ塩基のビス(サリチルアルデヒド)−エチレンジアミンの残基であり;
RはHまたは電子供与置換基、例えば、CH3O−、C2H5O−、HO−または−CH3であり;
R’はHまたはハロゲンである)が、該ポリマー金属錯体として使用され得る。
本発明は、置換四座配位のシッフ塩基を有する新しいポリマー金属錯体を使用することによって、高比エネルギー容量を有する電極を提供し、またこの電極に基づいた電気化学コンデンサーを提供する。
ここで、Meは遷移金属であり;
Yは上記シッフ塩基での窒素の原子を結合する架橋基であり;
Rは官能基(X)O−、−COO(X)である電子供与置換基であって;これらの基で(X)はアルカリ金属、例えば、LiまたはNaであり;
R’はHまたはハロゲンである。
ここで、Meは遷移金属であり;
Yは上記シッフ塩基での窒素の原子を結合する架橋基であり;
Rは官能基(X)O−、−COO(X)の形態での電子供与置換基であって;これらの基で(X)は上記陽極のエネルギー蓄積酸化還元ポリマーの電子供与置換基の組成物に含有されるアルカリ金属であり;
R’はHまたはハロゲンであり;
しかも、上記化合物は次の構造を有する:
ここで、Meは遷移金属であり;
Yはシッフ塩基の窒素の原子と結合する架橋基であり;
Rは官能基H、CH3O−、C2H5O−、HO−、−CH3
の形態の電子供与置換基であり;
R’はHまたはハロゲンであり;
しかも、上記化合物は次の構造を有する:
上記コンデンサーは、図1に例示するように、ケース1、電極2および3、電解液4、リード端子5および6、セパレータ7からなる。
Claims (22)
- 請求項1に記載の電極であって、ここで前記アルカリ金属はLiまたはNaである、電極。
- 請求項2に記載の電極であって、ここで前記シッフ塩基の窒素の原子と結合する前記架橋基Yは、サレンを含み、該サレンはビス(サリチルアルデヒド)−エチレンジアミンの残基である、電極。
- 請求項2に記載の電極であって、ここでビス(サリチルアルデヒド)−テトラメチルエチレンジアミンの残基であるソールトメン(Saltmen)は、架橋基Yとして使用され、該架橋基はシッフ塩基の窒素の原子を結合する、電極。
- 請求項2に記載の電極であって、ここでビス(サリチルアルデヒド)−テトラメチルエチレンジアミンの残基であるソールトメン(Saltmen)は、架橋基Yとして使用され、該架橋基はシッフ塩基の窒素の原子を結合する、電極。
- 請求項2に記載の電極であって、ここで前記ポリマー金属錯体はNi、Pd、Co、Cu、およびFeからなる群より選択される遷移金属を含む、電極。
- 請求項2に記載の電極であって、ここで前記導電性基板はカーボンファイバーから作られ、そしてコンプレックスレリーフ表面を有する、電極。
- 請求項2に記載の電極であって、ここで前記導電性基板はカーボンから作られ、そして金属被覆を有する、電極。
- 請求項2に記載の電極であって、ここで前記導電性基板は金属から作られ、そしてコンプレックスレリーフ表面を有する、電極。
- 請求項2に記載の電極であって、ここで前記導電性基板はフィルム、多孔性構造またはフォーム(foam)として作られる電子伝導を有するポリマーから作られる、電極。
- ケースの内部に配置した陽極および陰極を収納する該ケースと、該電極間の空間を満たす電解液とを含む電気化学コンデンサーであって、ここで該陽極は請求項1〜10のいずれかに従って作られる、電気化学コンデンサー。
- 請求項11に記載のコンデンサーであって、ここで前記陰極は前記陽極の前記酸化還元ポリマーの電子供与置換基の組成物に含有されるアルカリ金属と同じアルカリ金属を含有する活性物質を含む、コンデンサー。
- 請求項11に記載のコンデンサーであって、ここで前記陰極は導電性基板と、該基板上に被覆されたエネルギー蓄積酸化還元ポリマーの層とを含み、該酸化還元ポリマーは、ポリ−[Me(R,R’−Y)]の群から選択される、置換四座配位のシッフ塩基を有するポリマー金属錯体を含み、
ここでMeは遷移金属であり;
Yは該シッフ塩基の窒素原子を結合する架橋基であり;
Rは官能基(X)O−、−COO(X)を含む電子供与置換基であり、この式で(X)は前記陽極の該エネルギー蓄積酸化還元ポリマーの電子供与置換基の組成物に含有されるアルカリ金属であり;R’はHまたはハロゲンであり;そしてここで
該ポリマー金属錯体は次の構造を有し、
この式でnは、2〜50000の範囲から選択される、コンデンサー。 - 請求項11に記載のコンデンサーであって、ここで前記陰極は導電性基板と、該基板上に被覆されたエネルギー蓄積酸化還元ポリマーの層とを含み、該酸化還元ポリマーは、ポリ−[Me(R,R’−Y)]の群から選択される、置換四座配位のシッフ塩基を有するポリマー金属錯体であって、
ここでMeは遷移金属であり;
Yは前記シッフ塩基の窒素の原子を結合する架橋基であり;
Rは官能基(X)O−、−COO(X)の形態での電子供与置換基であり、この式で(X)は前記陽極の該エネルギー蓄積酸化還元ポリマーの電子供与置換基の組成物に含有されるアルカリ金属であり;
R’は水素またはハロゲンであり;
さらに該化合物は次の構造を有し:
この式でnは2〜50000の範囲の任意の値であり得る、コンデンサー。 - 請求項11に記載のコンデンサーであって、ここで前記電解液は有機溶媒中の化合物の溶液であり、該化合物は0.01mol/l以上の濃度まで該溶液に溶解し、そして該化合物は−3.0〜+1.5Vの電位の範囲内で電気化学的に不活性なイオンを含んでいる、コンデンサー。
- 請求項15に記載のコンデンサーであって、ここで前記化合物は前記陽極の前記エネルギー蓄積酸化還元ポリマーの電子供与置換基に含有されるアルカリ金属の塩であり、該アルカリ金属の塩は過塩素酸塩、テトラフルオロホウ酸塩、およびヘキサフルオロリン酸塩からなる群より選択される、コンデンサー。
- 請求項15に記載のコンデンサーであって、ここで前記有機溶媒はアセトニトリル、ジメチルケトン、および炭酸プロピレンからなる群より選択される、コンデンサー。
- 請求項11に記載のコンデンサーであって、ここで前記電解液は安定剤を含む、コンデンサー。
- 請求項11に記載のコンデンサーであって、ここで前記電解液は該電解液をゲル様状態に変化させるためのシックナーを含む、コンデンサー。
- 請求項11に記載のコンデンサーであって、該コンデンサーはさらに前記電極間に配置されるセパレータを含み、該セパレータは該コンデンサーの内部空間を陰極と陽極に分割する、コンデンサー。
- 請求項11に記載のコンデンサーであって、ここで前記ケースは前記電解液の作用に抵抗する物質から作られる、コンデンサー。
- 請求項11に記載のコンデンサーであって、該コンデンサーはさらに電解液を注入するための装置、安全弁、および該コンデンサーの前記ケースに取り付けた留め部材を含む、コンデンサー。
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| Application Number | Priority Date | Filing Date | Title |
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| US51083803P | 2003-10-14 | 2003-10-14 | |
| PCT/IB2004/052091 WO2005036572A1 (en) | 2003-10-14 | 2004-10-14 | Electrode for energy storage devices and electrochemical supercapacitor based on said electrode |
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| JP2007508709A true JP2007508709A (ja) | 2007-04-05 |
| JP2007508709A5 JP2007508709A5 (ja) | 2010-02-25 |
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| US (1) | US7382603B2 (ja) |
| EP (1) | EP1678728B1 (ja) |
| JP (1) | JP4551897B2 (ja) |
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| AT (1) | ATE440372T1 (ja) |
| DE (1) | DE602004022693D1 (ja) |
| DK (1) | DK1678728T3 (ja) |
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| JP2008091132A (ja) * | 2006-09-29 | 2008-04-17 | Nippon Chemicon Corp | 電極活物質 |
| JP2008091134A (ja) * | 2006-09-29 | 2008-04-17 | Nippon Chemicon Corp | 電気化学素子用電極及びその製造方法、並びに電気化学素子 |
| JP2008124059A (ja) * | 2006-11-08 | 2008-05-29 | Toyota Motor Corp | 蓄電装置とその使用方法及び製造方法 |
| WO2012053553A1 (ja) * | 2010-10-21 | 2012-04-26 | 株式会社豊田中央研究所 | 非水系二次電池用電極、それを備えた非水系二次電池及び組電池 |
| US8795893B2 (en) | 2010-10-21 | 2014-08-05 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Nonaqueous secondary battery electrode, nonaqueous secondary battery including the same, and assembled battery |
| JPWO2012053553A1 (ja) * | 2010-10-21 | 2014-02-24 | 株式会社豊田中央研究所 | 非水系二次電池用電極、それを備えた非水系二次電池及び組電池 |
| US8758938B2 (en) | 2011-04-08 | 2014-06-24 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Negative electrode for lithium secondary battery and lithium secondary battery |
| WO2013008510A1 (ja) * | 2011-07-11 | 2013-01-17 | 株式会社Ihi | 電気二重層キャパシタ用材料 |
| JPWO2013008510A1 (ja) * | 2011-07-11 | 2015-02-23 | 株式会社Ihi | 電気二重層キャパシタ用材料 |
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| US8932758B2 (en) | 2012-04-20 | 2015-01-13 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Electrode active material, nonaqueous secondary battery electrode, and nonaqueous secondary battery |
| WO2019221233A1 (ja) * | 2018-05-18 | 2019-11-21 | 日本電信電話株式会社 | リチウム二次電池 |
| JP2019200951A (ja) * | 2018-05-18 | 2019-11-21 | 日本電信電話株式会社 | リチウム二次電池 |
Also Published As
| Publication number | Publication date |
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| JP4551897B2 (ja) | 2010-09-29 |
| DE602004022693D1 (de) | 2009-10-01 |
| ATE440372T1 (de) | 2009-09-15 |
| PL1678728T3 (pl) | 2010-01-29 |
| KR20070022630A (ko) | 2007-02-27 |
| DK1678728T3 (da) | 2009-12-14 |
| US20070065719A1 (en) | 2007-03-22 |
| US7382603B2 (en) | 2008-06-03 |
| HK1097952A1 (en) | 2007-07-06 |
| ES2332138T3 (es) | 2010-01-27 |
| KR101087212B1 (ko) | 2011-11-29 |
| PT1678728E (pt) | 2009-11-24 |
| EP1678728B1 (en) | 2009-08-19 |
| WO2005036572A1 (en) | 2005-04-21 |
| EP1678728A1 (en) | 2006-07-12 |
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