JP3902611B2 - リチウム電池用負極組成物とそれを採用した負極及びリチウム電池 - Google Patents
リチウム電池用負極組成物とそれを採用した負極及びリチウム電池 Download PDFInfo
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Description
1)が溶解されたカソライト、有機硫黄及び(C2Sx)y(xは2.5−20,y>=2)よりなる群から選択された一つ以上を含む。
天然黒鉛97重量%、カルボキシメチルセルロース(CMC)1.0重量%、SBR 1.0重量%、ポリメタクリレート1.0重量%を水と共に混合した後、セラミックボールを入れて約10時間混錬させた。この混合物を厚さ12μmの銅箔上に300μm間隔のドクターブレードでキャスティングして負極を得た。これを約90℃のオーブンに入れて約10時間乾燥して得られた極板を再びロールプレッシングし、所定寸法で切断して120μm厚さの負極板を製造した。
天然黒鉛97重量%、CMC 1.0重量%、SBR 1.0重量%、ポリアクリレート1.0重量%を水と共に混合したことを除いて、実施例1と同じ方法を使用して負極板を製造した。
天然黒鉛95重量%、CMC 2.0重量%、SBR 2.0重量%、ポリメタクリレート1.0重量%を水と共に混合したことを除いて、実施例1と同じ方法を使用して負極板を製造した。
天然黒鉛96重量%、CMC 1.5重量%、SBR 1.0重量%、シトレート0.9重量%、タルタル酸塩0.6重量%を水と共に混合したことを除いて、実施例1と同じ方法を使用して負極板を製造した。
天然黒鉛97重量%、CMC 1.0重量%、SBR 1.0重量%、ポリナトリウムアクリレート1.0重量%を水と共に混合したことを除いて、実施例1と同じ方法を使用して負極板を製造した。
天然黒鉛97重量%、CMC 1.0重量%、メチルメタアクリレートブタジエンゴム1.0重量%、ポリメタアクリレート1.0重量%を水と共に混合したことを除いて、実施例1と同じ方法を使用して負極板を製造した。
天然黒鉛97重量%、CMC 1.5重量%、SBR 1.5重量%を水と共に混合したことを除いて、実施例1と同じ方法を使用して負極板を製造した。
天然黒鉛98重量%、CMC 1.0重量%、SBR 1.0重量%を水と共に混合したことを除いて、実施例1と同じ方法を使用して負極板を製造した。
まず、正極はLiCoO2 96重量%、結合剤としてPVDF 2重量%及び電子の移動を改善するためのカーボン導電剤2重量%を混合し、ここにN−メチルピロリドン(NMP)100ml及びセラミックボールを付加した後、この混合物を200mlプラスチック瓶に入れて10時間よく混錬させた。そして、15μm厚さのアルミニウム箔上に250μm間隔のドクターブレードでキャスティングを実施して正極板を得た。これを約110℃のオーブンに入れて約12時間乾燥してNMPを完全に揮発させた後、これを再びロールプレッシングし、所定寸法で切断して厚さ95μmの正極板を製造した。
前記実施例1及び比較例1の負極板を利用して製造されたリチウム電池を0.2Cの電流で−10℃で放電を実施した場合において容量を測定し、その結果を図1に表した。図1に示されたように、実施例1の負極板を利用して製造されたリチウム電池は、低温での容量特性が優秀であった。これは、実施例1で使われたポリメタクリレートのような水溶性陰イオン系多電解物の分散性の向上効果によって極板の電気的特性が向上したことを表している。
極板の結合力評価は、幅4mmのステンレス製ロッドを極板に垂直配置し、このロッドにかかる垂直荷重を変化させつつ極板に垂直方向に掻いて、塗布膜が銅板から剥離する時の垂直荷重を測定した。塗布膜剥離強度として極板強度の結果値を下記の表1に表した。
実施例1ないし3及び比較例1及び2の負極板を利用して製造したリチウム二次電池に対して実施した寿命特性を図2に表した。図2は、標準容量1800mAhの円筒形リチウム二次電池を1C率で充放電を反復する時、200回反復したサイクル中の放電容量の変化を表している。本発明による実施例1ないし3の負極板を利用して製造されたリチウム二次電池の場合には、200サイクル後にも全て約1620mAh以上の放電容量を維持し、比較例1及び2の負極板を利用して製造されたリチウム二次電池の場合と比較して放電容量維持率、すなわち寿命特性にさらに優れた。
Claims (7)
- 負極活物質、合成ゴム系結合剤、セルロース系分散剤、及び水溶性陰イオン系多電解物を含み、
前記負極活物質が90ないし99重量% 、前記結合剤が1.0ないし3.0重量% 、前記分散剤が1.0ないし3.0重量% 、及び前記水溶性陰イオン系多電解物が0.2ないし2.0重量%の含量で含まれ、
前記水溶性陰イオン系多電解物は、チェーンに解離基を有する高分子化合物またはこれと類似な性質を有する化合物であって溶媒に溶解時に前記解離基が解離されてイオン化されることによって分子内に負電荷を有する化合物であり、
前記水溶性陰イオン系多電解物が、ポリナトリウムアクリレートであることを特徴とするリチウム電池用負極組成物。 - 前記合成ゴム系結合剤がスチレンブタジエンゴム、ニトリルブタジエンゴム、メチル(メタ) アクリレートブタジエンゴム、クロロプレンゴム、カルボキシ変性スチレンブタジエンゴム、変性ポリオルガノシロキサン系重合体、またはこれらの混合物であることを特徴とする請求項1に記載の負極組成物。
- 前記セルロース系分散剤がカルボキシメチルセルロース、カルボキシエチルセルロース、アミノエチルセルロース、オキシエチルセルロース、またはこれらの混合物であることを特徴とする請求項1に記載の負極組成物。
- 前記セルロース系分散剤がNa塩またはNH4塩に置換されたことを特徴とする請求項1に記載の負極組成物。
- 前記負極活物質が、天然黒鉛、人造黒鉛、コークスまたは炭素繊維の黒鉛質材料;Al、Si、Sn、Ag、Bi、Mg、Zn、In、Ge、Pb及びTiよりなる群から選択された一つ以上の元素を含む化合物;Al、Si、Sn、Ag、Bi、Mg、Zn、In、Ge、Pb及びTiよりなる群から選択された一つ以上の元素を含む化合物と前記黒鉛質材料との炭素の複合化物; またはリチウム含有窒化物; であることを特徴とする請求項1に記載の負極組成物。
- 請求項1ないし5のうち何れか一項に記載の負極組成物を採用したことを特徴とするリチウム電池用負極。
- 請求項6に記載の負極を採用したことを特徴とするリチウム電池。
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KR10-2003-0040085A KR100537613B1 (ko) | 2003-06-20 | 2003-06-20 | 리튬 전지용 음극 조성물과 이를 채용한 음극 및 리튬 전지 |
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JP3902611B2 true JP3902611B2 (ja) | 2007-04-11 |
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US (1) | US7459235B2 (ja) |
EP (1) | EP1489673B1 (ja) |
JP (1) | JP3902611B2 (ja) |
KR (1) | KR100537613B1 (ja) |
CN (1) | CN1574425A (ja) |
DE (1) | DE602004012658T2 (ja) |
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JP2003282147A (ja) * | 2002-03-26 | 2003-10-03 | Toshiba Battery Co Ltd | リチウムイオン二次電池 |
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- 2004-06-18 CN CNA2004100550370A patent/CN1574425A/zh active Pending
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EP1489673A1 (en) | 2004-12-22 |
DE602004012658D1 (de) | 2008-05-08 |
EP1489673B1 (en) | 2008-03-26 |
DE602004012658T2 (de) | 2009-05-20 |
KR20040110665A (ko) | 2004-12-31 |
US20040258991A1 (en) | 2004-12-23 |
JP2005011808A (ja) | 2005-01-13 |
US7459235B2 (en) | 2008-12-02 |
CN1574425A (zh) | 2005-02-02 |
KR100537613B1 (ko) | 2005-12-19 |
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