JP5771873B2 - 伝導性(導電性)高分子複合体を用いた高容量/高出力の電気化学エネルギー貯蔵素子 - Google Patents
伝導性(導電性)高分子複合体を用いた高容量/高出力の電気化学エネルギー貯蔵素子 Download PDFInfo
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Description
前記溶媒としては、使用したい伝導性高分子と溶解度指数が類似しているのが好ましい。使用可能な溶媒の非制限的な例としては、アセトン、テトラヒドロフラン、メチレンクロライド、クロロホルム、ジメチルホルムアミド、N−メチル−2−ピロリジノン、シクロヘキサン、水又はこれらの混合物などが挙げられる。
1−1.複合体(伝導性カーボン/伝導性高分子)の製造
伝導性高分子PEDOT(poly(ethylenedioxy)thiophene)水溶液に、カーボンナノチューブ(厚さ:20nm、長さ:5μm)2wt%を分散させた後、分散度を向上させるために溶液の酸性度を3に変化させて固定した。均一に混合されたPEDOT/カーボンナノチューブスラリーを凝結乾燥過程によりPEDOT/カーボンナノチューブ複合体を製造した。このとき、最終の複合体粒子の直径は500nm範囲であった。
電極活物質として活性炭素(MSP20、関西熱化学株式会社)85wt%、導電剤として球状の粒子でありながら500nmのサイズを有するスーパー−p(カーボンブラック)5wt%、非伝導性バインダーとしてPTFE 5wt%、前記実施例1−1で製造されたPEDOT/CNT複合体5wt%を、溶剤である蒸溜水に添加して5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)薄膜及び負極集電体である銅薄膜に塗布及び乾燥して、正極及び負極として用いた。
前記正極、分離膜、負極フィルムをスタッキング(stacking)方式により組立て、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)が溶解されたプロピレンカーボネート(PC)を注入して、単位セルを有する電気二重層キャパシタを製造した。
電極活物質として活性炭素95wt%、前記実施例1−1で製造されたPEDOT/CNT複合体5wt%を用いて製造した外は、前記実施例1と同様な方法により電気二重層キャパシタを製造した。製造された実施例2のキャパシタの性能は、前記実施例1のキャパシタとほぼ対等であった。
電極活物質として活性炭素75wt%、導電剤としてスーパー−p 10wt%、非伝導性バインダーとしてPTFE 15wt%を用い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気二重層キャパシタを製造した。
PEDOT/CNT複合体の代りに、伝導性高分子PEDOTだけを用い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気二重層キャパシタを製造した。
PEDOT/CNT複合体の代りに、伝導性カーボン(CNT)を用いて電極を製造した以外は、前記実施例1と同様な方法を遂行した。しかしながら、電極フィルムの剥離現象が激しくて電気二重層キャパシタを製造できなかった。
実施例1の複合体粒子を含む電極の接着力テストを以下のように遂行した。その対照群として従来の通常のバインダーを備える比較例1の電極と、伝導性ナノ粒子と伝導性高分子とをそれぞれ単独に使用する比較例2及び比較例3の電極とを用いた。
本発明の複合体粒子を含む電気化学素子の性能を以下のように評価した。
実施例1及び実施例2で製造された電気二重層キャパシタを用いて充放電を進行し、以後、充放電の回数に従う放電容量挙動を測定した(図2及び図5参照)。
実施例1、比較例1及び比較例2で製造された電気二重層キャパシタを用いて放電比蓄電容量及び放電速度に従う比蓄電容量挙動を観察した。
Claims (14)
- (a)電極活物質、
(b)(i)導電性高分子粒子及び(ii)前記導電性高分子より高い導電性を有する無機物ナノ粒子が(i):(ii)=50〜99.9:50〜0.01の重量比からなり、
前記導電性高分子粒子の表面、内部又はこれらの全部に導電性無機物ナノ粒子が散布されてなり、直径が100〜1000nmである複合体粒子、
(c)非導電性バインダー、及び
(d)導電剤を含んでなり、
(b)前記複合体粒子を構成する導電性高分子が、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)、ポリアセチレン、ポリフェニレン及びポリチエニレンビニレンからなる群より選ばれる一種以上であり、
(i)前記導電性高分子粒子及び(ii)前記無機物ナノ粒子は、それぞれ電極物質の総重量に対して0.01〜10重量%の含有量で含まれ、
(c)前記非導電性バインダー及び(d)前記導電剤が、それぞれ電極物質の総重量に対して0重量%以上10重量%未満の含有量で含まれ、
(b)前記複合体粒子は、(a)前記電極活物質の粒子の間に散布されていることを特徴とする、電極。 - 前記電極が、吸脱着式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1に記載の電極。
- 前記電極における導電性高分子の含量が、電極物質100重量部当り0.01〜10重量部であることを特徴とする、請求項1又は2に記載の電極。
- 前記電極における導電性無機物ナノ粒子の含量が、電極物質100重量部当り0.01〜10重量部であることを特徴とする、請求項1〜3の何れか一項に記載の電極。
- 電気化学素子であって、
正極、負極、分離膜及び電解質を備えてなり、
前記正極、前記負極、又は前記正極及び前記負極の両電極が、請求項1〜4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、電荷が両電極の表面に吸脱着してエネルギーを貯蔵する方式によることを特徴とする、請求項5に記載の電気化学素子。
- 前記導電性無機物ナノ粒子が、球状、チューブ状、ファイバー状、ロッド状又は板状であることを特徴とする、請求項1〜4の何れか一項に記載の電極。
- 前記球状の導電性無機物ナノ粒子の直径が、0.1〜500nmであることを特徴とする、請求項7に記載の電極。
- 前記チューブ状、ファイバー状、ロッド状又は板状の導電性無機物ナノ粒子の厚さが0.1〜500nmであり、長さが0.01〜5μmであることを特徴とする、請求項7又は8に記載の電極。
- 前記導電性無機物ナノ粒子が、金属、金属酸化物、金属合金、炭素材からなる群より選ばれる一種以上であることを特徴とする、請求項1〜4の何れか一項に記載の電極。
- 前記導電性高分子の分子量(Mw)が、1,000〜1,000,000であることを特徴とする、請求項1〜4の何れか一項に記載の電極。
- 前記導電性高分子が、分散媒又は素子用溶媒に含浸時にゲル化することを特徴とする、請求項1〜4の何れか一項に記載の電極。
- 前記電極が、ドパントの投入により電子導電性が改質されることを特徴とする、請求項1〜4の何れか一項に記載の電極。
- 前記導電性無機物ナノ粒子、導電性高分子又はこれらの全部が、電荷を吸着する電極活物質としての役割を遂行できることを特徴とする、請求項1〜4の何れか一項に記載の電極。
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