JP2014041824A - 高電子伝導性高分子及びこれを用いた高用量/高出力電気エネルギー貯蔵素子 - Google Patents
高電子伝導性高分子及びこれを用いた高用量/高出力電気エネルギー貯蔵素子 Download PDFInfo
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Abstract
【解決手段】伝導性高分子に前記高分子の繰返し単位内に移動性電荷キャリアを導入するドーパントがドープされるが、前記ドーパントをドープしながら、高分子が持つ伝導帯以上の電圧を印加して電子伝導度を改質することを特徴とする高電子伝導性高分子の製造方法、前記製造方法により製造された高電子伝導性高分子、前記高電子伝導性高分子を含む電極及び前記電極を備える電気化学素子を提供する。前記伝導性高分子が、ポリアニリン、ポリピロール、ポリチオフェン、ポリ(エチレンジオキシ)チオフェン)]、ポリパラフェニレン、ポリアセチレン、ポリチエニレンビニレン及びポリフェニレンからなる群より選ばれた伝導性高分子である
【選択図】図1
Description
1−1. 塩投入/電圧印加による伝導性特性が向上した伝導性高分子の製造
伝導性高分子PEDOT(poly(ethylenedioxy)thiophene)(Mw:30,000;接着力:10g/cm以上;伝導度:〜1(10−5S/cm)フィルムを白金板にコートした後、2wt%のHCl溶液に浸漬した状態で、Ag/AgClに対し1Vを1時間加えてドープしたPEDOTを製造した。カウンター電極としては白金を用いた。
活物質として活性炭素(MSP20、関西熱化学株式会社)90wt%、前記実施例1−1で改質された伝導性高分子PEDOT 10wt%を、溶剤である蒸溜水に添加して2成分系混合物スラリーを製造した。前記混合物スラリーを正極集電体である20μm程度の厚さを有するアルミニウム(Al)薄膜に塗布及び乾燥して電極を製造し、正極及び負極は同じ電極を用いた。
前記正極、負極フィルムをスタッキング方式で組立て、組み立てられた電池に1Mのテトラフルオロほう酸テトラエチルアンモニウム(TEABF4)が溶解された炭酸プロピレン(PC)を注入して、電気化学素子を製造した。
活物質として活性炭素75wt%、導電剤としてスーパー−p(carbon black) 10wt%、結合剤としてPTFE 15wt%を、溶剤である蒸溜水に添加して3成分系混合物スラリーを製造した後、集電体に塗布及び乾燥して電極を製造した以外は、前記実施例1と同様な方法により電極及び電気化学素子を製造した。
ドーピング前の伝導性高分子PEDOTを用いた以外は、前記実施例1と同様な方法により電極及び電気化学素子を製造した。
電圧印加なしに塩投入だけでドーピング特性が向上したPEDOTを用いた以外は、前記実施例1と同様な方法により電極及び電気化学素子を製造した。
実施例1で改質された高電子伝導性高分子(PEDOT)を用い、その対照群としてリチウム二次電池及び電気二重層キャパシタの導電剤として用いられるスーパー−p及び一般的に電子伝導度が高いと評価されるカーボンナノチューブ(CNT)をそれぞれ用いた。これらをそれぞれペレット化した後、4探針法を用いて電子伝導度を測定した。
実施例1及び比較例1〜比較例3の電極を用いた。各電極の電極層にテープを貼付及び剥離することにより、接着力比較テストを進行し、以後、テープをとり除いた以後テープに残っている電極活物質階の程度(電極のしみの程度)を下記表2に示す。
実施例1及び比較例1〜比較例3で製造された吸脱着方式の電気化学素子を用いて放電容量を比較し、その結果を図3に示す。
Claims (16)
- 伝導性高分子に前記高分子の繰返し単位内に移動性電荷キャリアを導入するドーパントがドープされるが、前記ドーパントをドープしながら、高分子が持つ伝導帯以上の電圧を印加して電子伝導度を改質することを特徴とする、高電子伝導性高分子の製造方法。
- 前記伝導性高分子が、改質前の伝導性高分子の電子伝導度より100%以上向上することを特徴とする、請求項1に記載の製造方法。
- 前記ドーパントが、イオン化可能な塩化合物であることを特徴とする、請求項1又は2に記載の製造方法。
- 前記ドーパントが、酸、酸化剤及び還元剤からなる群より選ばれることを特徴とする、請求項1又は2に記載の製造方法。
- 前記ドーパントが、Na、K、Li、Caに置換又は非置換されたスルホン酸、PF6 −、BF6 −、Cl−、SO4 2−、ClO4 −、F−を含む遷移金属塩、I2、AsF6、LiBF4、炭素数1〜6のアルキルハライド、炭素数1〜6のアリールハライド及び酸無水物からなる群より選ばれることを特徴とする、請求項1又は2に記載の製造方法。
- 前記ドーパントの含量が、伝導性高分子100モル当り30〜50モルであることを特徴とする、請求項1〜5の何れか一項に記載の製造方法。
- 前記伝導性高分子が、ポリアニリン、ポリピロール、ポリチオフェン、PEDOT[poly(ethylenedioxy)thiophene:ポリ(エチレンジオキシ)チオフェン)]、ポリパラフェニレン、ポリアセチレン、ポリチエニレンビニレン及びポリフェニレンからなる群より選ばれることを特徴とする、請求項1〜6の何れか一項に記載の製造方法。
- 請求項1〜7の何れか一項の製造方法により製造されることを特徴とする、伝導性高分子。
- 前記伝導性高分子が、高分子の繰返し単位に存在する移動性電子1個当り移動性電荷キャリアを0.1〜1の範囲にドープすることを特徴とする、請求項8に記載の伝導性高分子。
- 前記伝導性高分子が、接着力が10g/cm以上であり、伝導度が10−5〜105S/cmの範囲であることを特徴とする、請求項8又は9に記載の伝導性高分子。
- 集電体上に電極活物質層が結着された電極であって、
前記電極活物質層が、
(a)電極活物質、及び、
(b)請求項8〜10の何れか一項に記載の伝導性高分子を備えてなることを特徴とする、電極。 - 前記伝導性高分子が、導電剤、バインダー及び電極活物質の何れか一つ以上の役割を遂行できることを特徴とする、請求項11に記載の電極。
- 前記電極が、吸脱着方式の電気エネルギー貯蔵素子用電極であることを特徴とする、請求項11又は12に記載の電極。
- 前記伝導性高分子が、電極活物質層を構成する総物質100重量部当り0.01〜90重量部であることを特徴とする、請求項11〜13の何れか一項に記載の電極。
- 電気化学素子であって、
正極と、負極と、分離膜と、及び電解質を備えてなり、
前記正極、負極、又は両電極が、請求項11〜14の何れか一項に記載の電極であることを特徴とする、電気化学素子。 - 前記電気化学素子が、リチウム二次電池及び電気化学的キャパシタからなる群より選ばれることを特徴とする、請求項15に記載の電気化学素子。
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JP2009176719A (ja) * | 2007-12-26 | 2009-08-06 | Sony Corp | 電解液、二次電池およびスルホン化合物 |
WO2010028162A2 (en) * | 2008-09-04 | 2010-03-11 | The Regents Of The University Of California | Charge storage device architecture for increasing energy and power density |
EP2692796B1 (en) * | 2011-03-28 | 2019-07-10 | Sumitomo Chemical Co., Ltd | Composition |
EP2706584A1 (en) * | 2012-09-07 | 2014-03-12 | Novaled AG | Charge transporting semi-conducting material and semi-conducting device |
KR101426493B1 (ko) | 2013-05-09 | 2014-08-05 | 국민대학교산학협력단 | 의사-커패시터용 전도성 고분자 중공 나노구 제조방법 |
CN103360709A (zh) * | 2013-06-25 | 2013-10-23 | 辅讯光电工业(苏州)有限公司 | 多功能光学膜及其组成物、多功能光学板及其制造方法 |
KR101402851B1 (ko) | 2013-07-11 | 2014-06-02 | 광주과학기술원 | 폴리아닐린 및 폴리피롤을 포함하는 전도성 네트워크 복합체 및 그 제조방법 |
JP6814945B2 (ja) * | 2015-11-27 | 2021-01-20 | パナソニックIpマネジメント株式会社 | 電気化学デバイスおよびその製造方法 |
CN110105549A (zh) * | 2019-04-23 | 2019-08-09 | 上海萃励电子科技有限公司 | 一种MnO2负载聚3-烷基噻吩的合成方法 |
JPWO2020262443A1 (ja) * | 2019-06-28 | 2020-12-30 | ||
KR102311271B1 (ko) * | 2020-02-14 | 2021-10-13 | 광주과학기술원 | 전도성 고분자가 코팅된 전극재 |
CN114005971B (zh) * | 2021-10-22 | 2024-04-19 | 陕西红马科技有限公司 | 一种具有p-型掺杂导电高分子涂层的正极材料及其制备方法 |
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JP2009537061A (ja) | 2009-10-22 |
EP2027588A4 (en) | 2010-07-28 |
JP5999367B2 (ja) | 2016-09-28 |
WO2007133017A1 (en) | 2007-11-22 |
CN101443857B (zh) | 2013-06-05 |
CN101443857A (zh) | 2009-05-27 |
KR20070109940A (ko) | 2007-11-15 |
EP2027588A1 (en) | 2009-02-25 |
EP2027588B1 (en) | 2017-01-18 |
US20100151319A1 (en) | 2010-06-17 |
KR100812063B1 (ko) | 2008-03-07 |
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