JP2007520032A - イオン性液体によって改質された正極及びこれを含む電気化学素子 - Google Patents
イオン性液体によって改質された正極及びこれを含む電気化学素子 Download PDFInfo
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Abstract
Description
BDMI-PF6及びLiPF6をそれぞれプロピレンカーボネート(PC)に溶解させて電解液を製造したし、この電解液の濃度は0.25Mないし1.5Mの範囲で調節した。各溶液をPFG-NMR(pulsed field gradient-NMR、Bruker DRX-600 spectrometer)によってイオン分散係数(ionic diffusion coefficient)を測定した。
実施例1
1-1.正極
正極活物質であるLiCoO2、導電剤であるカーボンブラック、バインダーであるポリビニリデンフロライド(PVdF)を94:3:3の重量比で混合して、ここにイオン性液体であるBDMI-PF6を前記正極活物質100重量部当りに3重量部を投入して混合した。得られた混合物にN-メチルピロリドン(NMP)を加えてスラリーを製造した。製造されたスラリーをアルミニウムフォイルに塗布して、130℃で2時間の間に熱処理して正極を製造した。このように製造された正極を圧延した後、1.4875cm2でパンチングした。
前記実施例1-1で製造された正極、Li金属箔(metal)を1.767cm2にパンチングして用意した負極を使用したし、前記両電極との間にポリエチレン樹脂分離膜を配置した後(図1参照)、1MLiPF6を含んで、EC:PC:DECが3:2:5の重量比である電解液を注入してコインセルを製造した。
イオン性液体であるBDMI-PF6の代わりにBMI-PF6を使用したことを除き、前記実施例1と同一な方法を遂行して正極及びリチウム二次電池を製造した。
イオン性液体であるBDMI-PF6の代わりにTMHA-PF6を使用したことを除き、前記実施例1と同一な方法を遂行して正極及びリチウム二次電池を製造した。
イオン性液体であるBDMI-PF6の代わりにTMHA-TFSIを使用したことを除き、前記実施例1と同一な方法を遂行して正極及びリチウム二次電池を製造した。
比較例1
イオン性液体を添加しないで活物質、導電剤及びバインダーの割合を94:3:3の重量比で調節した正極スラリーを使用したことを除き、前記実施例1と同一な方法を遂行して正極及びリチウム二次電池を製造した。
イオン性液体を添加しないで活物質、導電剤及びバインダーの割合を94:3:3の重量比で調節した正極スラリーを使用して正極を製造した後、1Mのリチウムヘキサフロロポスペイト(LiPF6)が溶解されたEC:PC:DEC(=3:2:5の重量比)系の電解液重量部当りBMI-PF6 3重量部を添加したことを除き、前記実施例1と同一な方法を遂行してリチウム二次電池を製造した。
イオン性液体を添加しないで活物質、導電剤及びバインダーの割合を94:3:3の重量比で調節した正極スラリーを使用して正極を製造した後、1Mのリチウムヘキサフロロポスペイト(LiPF6)が溶解されたEC:PC:DEC(=3:2:5の重量比)系の電解液100重量部当りBMI-PF6 10重量部を添加したことを除き、前記実施例1と同一な方法を遂行してリチウム二次電池を製造した。
本発明によってイオン性液体で改質された正極を具備したリチウム二次電池の性能を評価するため、下記のような実験を実施した。
本発明によってイオン性液体に改質された正極を具備したリチウム二次電池の安全性を評価するために、下記のような実験を実施した。
Claims (9)
- 正極スラリーから製造された正極であって、
(a)リチウム含有金属複合酸化物、またはカルコゲナイド化合物系列の正極活物質と、及び
(b)イオン性液体とを含んでなる、正極。 - 前記イオン性液体の陽イオンが、炭素数1ないし15であるアルキル基によって置換されるか、または非置換されたイミダゾリウム、ピラゾリウム、リアゾリウム、チアゾリウム、オキサゾリウム、ピリダジニウム、ピリミリウム、ピラジニウム、アンモニウム、ホスホニウム、ピリジニウム及びピロリジニウムからなる群から選択された少なくとも一種である、請求項1に記載の正極。
- 前記イオン性液体の陰イオンが、PF6 -、BF4 -、CF3SO3 -、N(CF3SO2)2 -、N(C2F5SO2)2 -、C(CF2SO2)3 -、AsF6 -、SbF6 -、AlCl4 -、NbF6 -、HSO4 -、ClO4 -、CH3SO3 -、CF3CO2 -からなる群から選択された少なくとも一種である、請求項1に記載の正極。
- 前記イオン性液体が、両性イオン系列の化合物である、請求項1に記載の正極。
- 前記イオン性液体の添加量が、正極活物質100重量部対比0.1ないし30重量部の範囲である、請求項1に記載の正極。
- 前記リチウム含有金属複合酸化物系列の化合物が、アルカリ金属、アルカリ土金属、13族元素、14族元素、15族元素、転移金属及び希土類元素からなる群から選択された少なくとも一種の元素を含むリチウム含有酸化物である、請求項1に記載の正極。
- 前記カルコゲナイド系列の化合物が、TiS2、SeO2、MoS2、FeS2、MnO2、NbSe3、V2O5、V6O13、CuCl2からなる群から選択された少なくとも一種以上である、請求項1に記載の正極。
- 電気化学素子であって、
(a)請求項1ないし請求項7のうちいずれか一項に記載された正極と、
(b)負極と、
(c)分離膜と、及び
(d)電解液とを備えてなる、電気化学素子。 - 前記電気化学素子が、リチウム二次電池である、請求項8に記載の電気化学素子。
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PCT/KR2004/003434 WO2005064712A1 (en) | 2003-12-30 | 2004-12-24 | Ionic liquid-modified cathode and electrochemical device using the same |
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JP2009176519A (ja) * | 2008-01-23 | 2009-08-06 | Sony Corp | 非水電解質電池および電極ならびにそれらの製造方法 |
WO2009107875A1 (ja) | 2008-02-29 | 2009-09-03 | 住友化学株式会社 | イオン液体を含む電極膜及び電極、それらの製造方法、並びに蓄電デバイス |
US8372546B2 (en) | 2008-02-13 | 2013-02-12 | Sony Corporation | Non-aqueous electrolyte battery and method for manufacturing the same |
JP2015509265A (ja) * | 2011-12-30 | 2015-03-26 | サムスン ファイン ケミカルズ カンパニー リミテッドSamsungfine Chemicals Co.,Ltd | リチウム二次電池用の正極活物質、その製造方法およびそれを含むリチウム二次電池 |
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JP4598001B2 (ja) | 2010-12-15 |
TWI262614B (en) | 2006-09-21 |
CN1902775A (zh) | 2007-01-24 |
TW200527731A (en) | 2005-08-16 |
US7316866B2 (en) | 2008-01-08 |
CN100481584C (zh) | 2009-04-22 |
KR100584680B1 (ko) | 2006-05-29 |
WO2005064712A1 (en) | 2005-07-14 |
EP1702374A4 (en) | 2007-10-24 |
KR20050071347A (ko) | 2005-07-07 |
EP1702374B1 (en) | 2015-11-18 |
US20050175898A1 (en) | 2005-08-11 |
EP1702374A1 (en) | 2006-09-20 |
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