JP2008547156A - 大容量不可逆物質を含有する新規なリチウムイオン電池システム - Google Patents
大容量不可逆物質を含有する新規なリチウムイオン電池システム Download PDFInfo
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Abstract
Description
一般式I
LI2+xNI1−yMyO2+α
上記式中、−0.5<x<0.5、0<y<1、0<α<0.3、Mは、P、B、C、Al、Sc、Sr、TI、V、Zr、Mn、Fe、Co、Cu、Zn、Cr、Mg、Nb、Mo、及びCdからなる群より選ばれた1種以上の元素である。
[1]リチウムイオンを吸蔵、放出することができる正極と、
[2]リチウムイオンを吸蔵、放出することができる負極と、
[3]多孔性セパレータ、及び
[4]a)リチウム塩、b)電解液溶媒と、を含んでなる。
実施例1
正極活物質100重量部に対して、LI2NIO2 77重量部とMnO2 23重量部の混合物を正極活物質として用いた。上記正極活物質80重量%、導電剤としてのKS-6 10重量%、及び結合剤としてのPVdF10重量%を溶剤のNMPに添加して正極スラリーを調製した後、Al集電体上にコーティングして正極を作製した。
LI2NIO2:MoO3=77:23の重量比で混合してなるものを正極活物質として用い、カーボンを負極活物質として用いたことを除いては、実施例1と同法にてコイン形フル電池を作製し、該フル電池に対して1.5〜4.2Vの電圧範囲で充放電試験を実施し、その充放電プロパイルを図3に示した。
LICoO2 80%、KS-6(導電剤)10重量%、及びPVdF(結合剤)10重量%を溶剤であるNMPに添加して正極スラリーを調製した後、Al集電体上にコーティングして正極を作製し、LI金属を用いて負極を作製し、該両電極でコイン形半電池を作製した後、該半電池に対して1.5〜4.25Vの電圧範囲で充放電試験を実施した。該半電池の容量を図5に示した。
実施例1及び2から分かるように、本発明によれば、初回サイクルの充電時にリチウムイオンを過量放出することができる大容量不可逆物質であるLI2NIO2とリチウムを含有していない金属酸化物であるMnO2またはMoO3とを含む混合正極と、リチウム金属に代えてカーボンを含む負極を用いてコイン形フル電池を作製することができ、図2及び図4に示すように、MnO2+LI2NIO2(実施例1)、MoO3+LI2NIO2(実施例2)の混合正極の重量当たりの放電容量は、それぞれ292mAh/g、296mAh/gであって、本発明によるフル電池が、正極材料として既存から用いられていたリチウムコバルトオキシド、リチウムニッケルオキシド、またはリチウムマンガンオキシド(図5)を用いてなる電池に比べて優れた容量を示すことができる。
2:正極集電体
3:負極側のケース体
4:負極集電体
5:正極
6:負極
7:セパレータ
8:電解質
9:パッキング(または、ゲスケット)
Claims (13)
- リチウムを含有していない金属酸化物と、リチウムを含有した大容量不可逆物質とを含んでなることを特徴とする、正極活物質。
- 前記大容量不可逆物質が、初回サイクルの脱リチウム化時に不可逆的な相転移によって初期充電容量の50%以上が失われることを特徴とする、請求項1に記載の正極活物質。
- 前記リチウムを含有していない金属酸化物と、前記リチウムを含有した大容量不可逆物質とが互いに混合されてなることを特徴とする、請求項1に記載の正極活物質。
- 前記大容量不可逆物質が、
Li2+xNi1−yMyO2+α
(上記式中、−0.5<x<0.5、0<y<1、0<α<0.3、Mは、P、B、C、Al、Sc、Sr、Ti、V、Zr、Mn、Fe、Co、Cu、Zn、Cr、Mg、Nb、Mo、及びCdからなる群より選ばれた1種以上の元素である。)、
LiMnO2、LiMxMn1−xO2
(上記式中、xは、0.05<x<0.5であり、Mは、Cr、Al、Ni、Mn、及びCoからなる群より選ばれる。)、
LixVO3(1<x<6)、Li3Fe2(PO4)3、Li3Fe2(SO4)3、Li3V(PO4)3からなる群より選ばれた1種以上の化合物であることを特徴とする、請求項1に記載の正極活物質。 - 前記大容量不可逆物質が、下記一般式I:
Li2+xNi1−yMyO2+α (I)
(上記式中、−0.5<x<0.5、0<y<1、0<α<0.3、
Mは、P、B、C、Al、Sc、Sr、Ti、V、Zr、Mn、Fe、Co、Cu、Zn、Cr、Mg、Nb、Mo、及びCdからなる群より選ばれた1種以上の元素である。)
で示される化合物であり、
該一般式Iで示される化合物が、空間群Immmに属し、そのうち、Ni、Mの複合酸化物が平面四配位(Ni、M)O4を形成し、平面四配位構造が向かい合う辺(O−Oで形成された辺)を共有し、直鎖を形成していることを特徴とする、請求項1に記載の正極活物質。 - 前記リチウムを含有していない金属酸化物が、充放電容量が70mAh/g〜500mAh/gの範囲であることを特徴とする、請求項1に記載の正極活物質。
- 前記リチウムを含有していない金属酸化物が、MnO2、MoO3、VO2、V2O5、V6O13、Cr3O8、CrO2、Al2O3、ZrO2、AlPO4、SiO2、TiO2、MgOからなる群より選ばれた1種以上であることを特徴とする、請求項1に記載の正極活物質。
- 前記正極活物質100重量部に対して、前記大容量不可逆物質40〜80重量部と、前記リチウムを含有していない金属酸化物20〜60重量部を含んでなることを特徴とする、請求項1に記載の正極活物質。
- 前記正極活物質は、初回サイクルでの充電容量、放電容量ともに150mAh/g以上であることを特徴とする、請求項1に記載の正極活物質。
- 請求項1〜9のいずれか一項に記載の正極活物質を用いてなることを特徴とする、正極。
- 請求項1〜9のいずれか一項に記載の正極活物質を正極に含むことを特徴とする、リチウムイオン電池。
- リチウムを含有していないがリチウムイオンを吸蔵及び放出することができる物質を負極活物質として用いることを特徴とする、請求項11に記載のリチウムイオン電池。
- カーボンを負極活物質として用いることを特徴とする、請求項12に記載のリチウムイオン電池。
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KR20050033466 | 2005-04-22 | ||
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PCT/KR2006/001485 WO2006112674A1 (en) | 2005-04-22 | 2006-04-20 | New system of lithium ion battery containing material with high irreversible capacity |
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JP2020526893A (ja) * | 2017-08-28 | 2020-08-31 | エルジー・ケム・リミテッド | リチウム二次電池 |
JP7044861B2 (ja) | 2017-08-28 | 2022-03-30 | エルジー エナジー ソリューション リミテッド | リチウム二次電池 |
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JP2022540661A (ja) * | 2020-01-31 | 2022-09-16 | エルジー エナジー ソリューション リミテッド | 二次電池用正極材に含まれる不可逆添加剤、それを含む正極材、および正極材を含む二次電池 |
JP7276979B2 (ja) | 2020-01-31 | 2023-05-18 | エルジー エナジー ソリューション リミテッド | 二次電池用正極材に含まれる不可逆添加剤、それを含む正極材、および正極材を含む二次電池 |
Also Published As
Publication number | Publication date |
---|---|
WO2006112674A1 (en) | 2006-10-26 |
EP1880436B1 (en) | 2017-07-19 |
TWI362136B (en) | 2012-04-11 |
TW200705737A (en) | 2007-02-01 |
US8846250B2 (en) | 2014-09-30 |
JP5318565B2 (ja) | 2013-10-16 |
KR20060111393A (ko) | 2006-10-27 |
EP1880436A1 (en) | 2008-01-23 |
CN101164186B (zh) | 2010-05-26 |
EP1880436A4 (en) | 2008-11-19 |
CN101164186A (zh) | 2008-04-16 |
US20060257737A1 (en) | 2006-11-16 |
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