JP4523807B2 - リチウム二次電池用正極活物質、その製造方法及びそれを含むリチウム二次電池 - Google Patents
リチウム二次電池用正極活物質、その製造方法及びそれを含むリチウム二次電池 Download PDFInfo
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Description
[化学式1]
LixNiyCozMn1-y-z-qXqO2
(前記化学式で、1.05≦x、0<y<0.35、0<z<0.35であり、XはAl、 Mg、Sr、TiまたはLaであり、q<0.1である)
[化学式1]
LixNiyCozMn1-y-z-qXqO2
(前記化学式で、1.05≦x、0<y<0.35、0<z<0.35であり、XはAl、 Mg、Sr、TiまたはLaであり、q<0.1である)
Ni1/3Co1/3Mn1/3(OH)2複合水酸化物(以下、前駆体)を、LiOH・H2Oと(Ni+Co+Mn):Liが1:1のモル比になるように混合した後、ボールミルを利用して約2時間程混合した。得られた混合物を空気中で温度480℃で5時間程度1次熱処理をした後、温度を常温まで徐々に下げた。30分程再混合をした後、温度1000℃で20時間続けて2次熱処理をした後、再び常温まで冷却してから、45μmの孔を有する篩に掛けてLi(Ni1/3Co1/3Mn1/3)O2正極活物質を製造した。この正極活物質に対する構造分析はXRDを実施した。
市販されるLiCoO2を正極活物質として用いた。
前駆体とLiOH・H2Oの比を1:1.15に変更してLi1.15(Ni1/3Co1/3Mn1/3)O2正極活物質を製造したことを除いては前記比較例1と同じに実施した。
前駆体とLiOH・H2Oの比を1:1.30に変更して2次熱処理工程を900℃で実施してLi1.30(Ni1/3Co1/3Mn1/3)O2正極活物質を製造したことを除いては前記比較例1と同じに実施した。
Ni1/3Co1/3Mn1/3(OH)2複合水酸化物(以下、前駆体)をLiOH・H2Oと(Ni+Co+Mn):Liが1:1.05のモル比になるように混合した後、ボールミルを利用して約2時間程混合した。得られた混合物を空気中の温度500℃で10時間程度1次熱処理をした後、温度を常温まで徐々に下げた。30分程再混合をした後、温度900℃で15時間2次熱処理をしてから、常温まで冷却し、45μmの孔を有する篩に掛けてLi1.05(Ni1/3Co1/3Mn1/3)O2正極活物質を合成した。
前駆体とLiOH・H2Oの比を1:1.15に変更してLi1.15(Ni1/3Co1/3Mn1/3)O2正極活物質を製造したことを除いては前記実施例1と同じに実施した。
前駆体とLiOH・H2Oの比を1:1.20に変更してLi1.20(Ni1/3Co1/3Mn1/3)O2正極活物質を製造したことを除いては前記実施例1と同じに実施した。
前駆体にNi0.32Co0.32Mn0.32Al0.04(OH)2を利用してLi1.05(Ni0.32Co0.32Mn0.32Al0.04)O2正極活物質を製造したことを除いては前記実施例1と同じに実施した。
2 セパレータ
3 正極
4 負極
5 ケース
Claims (13)
- 下記の化学式1で表示され、CuKα線を用いたX線の回折パターンにおいて、(003)面と(104)面のX線の回折強度比であるI(003)/I(104)が1.157乃至1.202であり、結晶構造において、a軸の長さが0.2851nm以上、0.2861nm未満であり、c軸の長さが1.420nm以上、1.423nm未満である、リチウム二次電池用正極活物質。
[化学式1]
LixNiyCozMn1−y−z−qXqO2
(前記化学式で、1.05≦x、0<y<0.35、0<z<0.35であり、XはAl、Mg、Sr、TiまたはLaであり、0≦q<0.1であり、y=z=1−y−z−qである。) - 前記正極活物質におけるNi、Co、Mnの合計量1モルに対してリチウムのモル比は1.05乃至1.25であることを特徴とする、請求項1に記載のリチウム二次電池用正極活物質。
- 前記正極活物質は、Ni(2P3/2)の結合エネルギーを示すXPSピークが854乃至855eV、856乃至856.6eV及び861.0乃至861.5eVで三つ現れることを特徴とする、請求項1又は2に記載のリチウム二次電池用正極活物質。
- 前記正極活物質は、Mn(2P3/2)の結合エネルギーを示すXPSピークが642.4乃至642.6eV及び643.5乃至644.1eVで二つ現れることを特徴とする、請求項1〜3のいずれか1項に記載のリチウム二次電池用正極活物質。
- リチウム包含化合物とニッケル、コバルト及びマンガンを含む化合物をニッケル、コバルト及びマンガンの合計量1モルに対してリチウムのモル比が1.05乃至1.25になるように混合し;
前記混合物を450乃至550℃で1次熱処理し;
前記1次熱処理生成物を800℃乃至900℃で2次熱処理する工程を含む、請求項1に記載のリチウム二次電池用正極活物質の製造方法。 - 前記1次熱処理工程を実施した後、1次熱処理生成物を常温まで徐々に冷却する工程をさらに実施することを特徴とする、請求項5に記載のリチウム二次電池用正極活物質の製造方法。
- 前記リチウム包含化合物は水酸化リチウム、硝酸リチウム及び酢酸リチウムからなる群より選択されることを特徴とする、請求項5又は6に記載のリチウム二次電池用正極活物質の製造方法。
- 前記ニッケル、コバルト及びマンガンを含む化合物は水酸化物、酸化物、硝酸塩及び硫酸塩からなる群より選択されることを特徴とする、請求項5〜7のいずれか1項に記載のリチウム二次電池用正極活物質の製造方法。
- 下記の化学式1で表示され、CuKα線を利用したX線回折パターンにおいて、(003)面と(104)面のX線回折強度比であるI(003)/I(104)が1.157乃至1.202であり、結晶構造において、a軸の長さが0.2851nm以上、0.2861nm未満であり、c軸の長さが1.420nm以上、1.423nm未満である、正極活物質を含む正極;
リチウムイオンを挿入及び脱離できる負極活物質を含む負極;及び
電解液を含むリチウム二次電池。
[化学式1]
LixNiyCozMn1−y−z−qXqO2
(前記化学式で、1.05≦x、0<y<0.35、0<z<0.35であり、XはAl、Mg、Sr、TiまたはLaであり、0≦q<0.1であり、y=z=1−y−z−qである。) - 前記負極活物質は炭素系列物質であることを特徴とする、請求項9に記載のリチウム二次電池。
- 前記正極活物質において、Li/(Ni+Co+Mn)のモル比は1.05乃至1.25であることを特徴とする、請求項9又は10に記載のリチウム二次電池。
- 前記正極活物質は、Ni(2P3/2)の結合エネルギーを示すXPSピークが854乃至855eV、856乃至856.6eV及び861.0乃至861.5eVで三つ現れることを特徴とする、請求項9〜11のいずれか1項に記載のリチウム二次電池。
- 前記正極活物質は、Mn(2P3/2)の結合エネルギーを示すXPSピークが642.4乃至642.6eV及び643.5乃至644.1eVで二つ現れることを特徴とする、請求項9〜12のいずれか1項に記載のリチウム二次電池。
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KR1020030049020A KR100560540B1 (ko) | 2003-07-18 | 2003-07-18 | 리튬 이차 전지용 양극 활물질, 그의 제조 방법 및 그를포함하는 리튬 이차 전지 |
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CN103762351A (zh) * | 2005-08-16 | 2014-04-30 | 株式会社Lg化学 | 阴极活性材料及包含该阴极活性材料的锂二次电池 |
KR100783294B1 (ko) * | 2005-08-16 | 2007-12-10 | 주식회사 엘지화학 | 양극 활물질 및 그것을 포함하고 있는 리튬 이차전지 |
JP5173145B2 (ja) * | 2006-02-08 | 2013-03-27 | 三洋電機株式会社 | 非水電解質二次電池 |
KR100820057B1 (ko) * | 2006-12-21 | 2008-04-07 | 주식회사 엘 앤 에프 | 리튬 이차 전지용 양극 활물질, 이의 제조방법 및 이를포함하는 리튬 이차 전지 |
EP2071650A4 (en) | 2007-03-30 | 2013-04-03 | Panasonic Corp | ACTIVE MATERIAL FOR A NON-AQUEOUS ELECTROLYTE SECONDARY BATTERY AND METHOD FOR THE PRODUCTION THEREOF |
EP2264814A4 (en) * | 2008-04-17 | 2016-08-17 | Jx Nippon Mining & Metals Corp | POSITIVE ELECTRODE ACTIVE MATERIAL FOR LITHIUM-ION BATTERY, POSITIVE ELECTRODE FOR RECHARGEABLE BATTERY, AND LITHIUM-ION BATTERY |
FR2937633B1 (fr) | 2008-10-24 | 2010-11-19 | Saft Groupe Sa | Materiau d'electrode positive pour accumulateur lithium-ion |
JP4873000B2 (ja) | 2008-12-05 | 2012-02-08 | ソニー株式会社 | 非水電解質二次電池用正極活物質および非水電解質二次電池 |
WO2010074313A1 (ja) * | 2008-12-24 | 2010-07-01 | 日本碍子株式会社 | リチウム二次電池の正極活物質用の板状粒子、及び同物質膜、並びにリチウム二次電池 |
US20100173204A1 (en) * | 2008-12-24 | 2010-07-08 | Ngk Insulators, Ltd. | Plate-like particle for cathode active material of a lithium secondary battery, a cathode active material film of a lithium secondary battery, method for manufacturing the same, method for manufacturing a cathode active material of a lithium secondary battery, and a lithium secondary battery |
CN102171864A (zh) | 2008-12-24 | 2011-08-31 | 日本碍子株式会社 | 锂二次电池的正极活性物质用的板状粒子、同物质膜及锂二次电池 |
WO2010074302A1 (ja) * | 2008-12-24 | 2010-07-01 | 日本碍子株式会社 | リチウム二次電池の正極活物質用の板状粒子、及び同物質膜、並びにリチウム二次電池 |
US8916293B2 (en) * | 2008-12-24 | 2014-12-23 | Ngk Insulators, Ltd. | Plate-like particle for cathode active material for lithium secondary battery, cathode active material film for lithium secondary battery, methods for manufacturing the particle and film, method for manufacturing cathode active material for lithium secondary battery, and lithium secondary battery |
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US7226698B2 (en) | 2007-06-05 |
KR20050010131A (ko) | 2005-01-27 |
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