JP2012059390A - 非水電解液電池 - Google Patents
非水電解液電池 Download PDFInfo
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- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
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- NXPZICSHDHGMGT-UHFFFAOYSA-N [Co].[Mn].[Li] Chemical compound [Co].[Mn].[Li] NXPZICSHDHGMGT-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
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- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
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- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
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- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- H—ELECTRICITY
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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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- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
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Abstract
【解決手段】リチウムイオン二次電池20では、電池容器7に、正負極板がセパレータを介して捲回された電極群6が収容されており、非水電解液が注液されている。正極板は、アルミニウム箔W1の両面に、リチウム遷移金属複酸化物を含む正極合剤層W2が形成されている。正極合剤層W2の表面には、難燃化剤のホスファゼン化合物と、イオン伝導性を有するバインダのポリエチレンオキサイドとを含む難燃化剤層W6が形成されている。負極板は、圧延銅箔W3の両面に、負極活物質の炭素材を含む負極合剤層W4が形成されている。ポリエチレンオキサイドでイオン伝導性が確保され、電池異常で電池温度が上昇するとホスファゼン化合物が分解する。
【選択図】図1
Description
実施例1では、難燃化剤のホスファゼン化合物(株式会社ブリヂストン製、商品名ホスライト(登録商標)、固体状、分解温度250℃以上)とポリエチレンオキサイドとを溶解、分散させた溶液を調製した。ポリエチレンオキサイドの配合割合は、正極合剤に対して1wt%に設定した。ホスファゼン化合物の配合割合は、下表1に示すように、正極合剤に対して1wt%に調整した。この分散溶液を、プレス加工により厚さを120μmに調整した正極合剤層W2の表面に塗布した。このとき、分散溶液の塗布量を調整することで、正極合剤に対する難燃化剤の配合割合を調整した。難燃化剤層W6の厚さは4μmとなった。難燃化剤層W6では、ホスファゼン化合物が50wt%、ポリエチレンオキサイドが50wt%でそれぞれ含まれることとなる。
表1に示すように、実施例2〜実施例9では、難燃化剤の配合割合を変える以外は実施例1と同様にした。すなわち、難燃化剤の配合割合は、実施例2では2wt%、実施例3では3wt%、実施例4では5wt%、実施例5では6wt%、実施例6では8wt%、実施例7では10wt%、実施例8では15wt%、実施例9では20wt%、にそれぞれ調整した。難燃化剤の配合割合を大きくするために正極合剤層W2に対する分散溶液の塗布量を増やしたことから、得られた正極板の難燃化剤層W6の厚さが変わることとなる。難燃化剤層W6の厚さは、表1に示すように、実施例2では8μm、実施例3では10μm、実施例4では17μm、実施例5では20μm、実施例6では24μm、実施例7では31μm、実施例8では44μm、実施例9では63μmとなった。また、難燃化剤層W6でのホスファゼン化合物およびポリエチレンオキサイドの割合は、実施例1と同様の分散溶液を使用し、塗布量により難燃化剤量を調整したことから、実施例2〜実施例9のいずれについても50wt%および50wt%となる。
比較例では、正極合剤層W2の表面に難燃化剤層W6を形成しない以外は実施例1と同様にした。すなわち、比較例のリチウムイオン二次電池は従来の電池である。
各実施例および比較例のリチウムイオン二次電池について、過充電試験を行い評価した。過充電試験では、電池中央部に熱電対を配置し、各リチウムイオン二次電池を0.5Cの電流値で充電し続けたときの電池表面の温度を測定した。過充電試験における電池表面最高温度を下表2に示す。
実施例10では、ホスファゼン化合物の配合割合を正極合剤に対して10wt%に設定し、ポリエチレンオキサイドの配合割合を、下表3に示すように、正極合剤に対して1wt%に調整したこと以外は実施例1と同様に、厚さ120μmの正極合剤層W2の表面に難燃化剤層W6を形成した。難燃化剤層W6の厚さは25μmとなった。難燃化剤層W6では、ホスファゼン化合物が91wt%、ポリエチレンオキサイドが9wt%でそれぞれ含まれることとなる。
表3に示すように、実施例11〜実施例14では、ポリエチレンオキサイドの配合割合を変える以外は実施例10と同様にした。すなわち、正極合材に対するポリエチレンオキサイドの配合割合は、実施例11では3wt%、実施例12では5wt%、実施例13では8wt%、実施例14では10wt%、にそれぞれ調整した。難燃化剤層W6の厚さは、実施例11では24μm、実施例12では26μm、実施例13では28μm、実施例14では31μm、となった。また、難燃化剤層W6でのホスファゼン化合物およびポリエチレンオキサイドの割合は、実施例11では77wt%および23wt%、実施例12では67wt%および33wt%、実施例13では56wt%および44wt%、実施例14では50wt%および50wt%、となる。
実施例15〜実施例16では、難燃化剤層W6のバインダを変える以外は実施例10と同様にした。すなわち、バインダとして、実施例15ではポリエチレングリコールジメチルエーテル、実施例16ではポリエチレングリコールメチルエーテルをそれぞれ用いた。表3に示すように、難燃化剤層W6の厚さは、実施例15では32μm、実施例16では29μmとなった。
実施例10〜実施例16および比較例のリチウムイオン二次電池について、充放電試験を行い評価した。充放電試験では、各リチウムイオン二次電池を0.5Cの電流値で充電した後、1.0Cおよび3.0Cの電流値で放電したときの放電容量を測定した。比較例のリチウムイオン二次電池における放電容量を100%としたときの相対容量を算出した。相対容量の結果を下表4に示す。
次に、本実施形態のリチウムイオン二次電池20の作用等について説明する。
W2 正極合剤層
W3 圧延銅箔(集電体)
W4 負極合剤層
W5 セパレータ
W6 難燃化剤層
6 電極群
20 円柱型リチウムイオン二次電池(非水電解液電池)
Claims (6)
- 活物質を含む正極合剤が集電体に塗着された正極板と、活物質を含む負極合剤が集電体に塗着された負極板とが多孔質セパレータを介して配置された非水電解液電池において、前記正極板、負極板およびセパレータの少なくとも1種の片面または両面に、難燃化剤のホスファゼン化合物およびイオン伝導性を有するバインダを含む難燃化剤層が配されたことを特徴とする非水電解液電池。
- 前記難燃化剤は60℃以上400℃以下の温度環境で熱分解することを特徴とする請求項1に記載の非水電解液電池。
- 前記難燃化剤は前記正極合剤に対して10wt%以上の割合で含有されていることを特徴とする請求項1に記載の非水電解液電池。
- 前記バインダはポリエーテル系高分子化合物であることを特徴とする請求項1に記載の非水電解液電池。
- 前記ポリエーテル系高分子化合物はポリエチレンオキサイドを含むことを特徴とする請求項4に記載の非水電解液電池。
- 前記難燃化剤層には、前記難燃化剤が50wt%〜91wt%の範囲の割合、前記バインダが9wt%〜50wt%の範囲の割合でそれぞれ含まれていることを特徴とする請求項1に記載の非水電解液電池。
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CN103125045B (zh) | 2016-08-10 |
US20130252090A1 (en) | 2013-09-26 |
KR20140027043A (ko) | 2014-03-06 |
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EP2615681A4 (en) | 2014-07-16 |
JP5623199B2 (ja) | 2014-11-12 |
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US9515353B2 (en) | 2016-12-06 |
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