JP2021509220A - リチウム二次電池用正極活物質、その製造方法、およびこ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、およびこれを含むリチウム二次電池 Download PDFInfo
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Abstract
Description
[化学式1]
LiaNixCoyMnz(M)1−(x+y+z)Ob
前記化学式1で、0.8≦a≦1.3であり、1.8≦b≦2.2であり、0.8≦x≦0.92であり、0<y≦0.15であり、0<z≦0.1であり、0<x+y+z<1であり、ドーピング元素であるMはAl、Zr、およびBを含む。
「Ni88モル%前駆体の製造」
正極材の製造に先立ち、(Ni0.88Co0.095Mn0.025)(OH)2組成を有する前駆体は、一般的な共沈法により製造した。
Core−shell gradient(Ni0.88Co0.095Mn0.025)(OH)2組成を有する大粒径および小粒径前駆体と、LiOH・H2O(SAMCHUN CHEMICAL、battery grade)を1:1.05モル比に混合した。
「Zr、およびAlだけがco−dopingされたCSG Ni 88%正極材の製造」
比較のためにBをドーピングせずにZrとAlだけがco−dopingされたNi88正極材を製造した。製造法は実施例と同一であり、この時、大/小粒径の全てが適用された。
「電気化学特性評価方法」
CR2032コインセルを利用して電気化学評価を進行した。極板製造用スラリーは、正極:導電剤(denka black):バインダー(PVDF、KF1100)=92.5:3.5:4wt%であり、固形分が約30%になるようにNMP(N−Methyl−2−pyrrolidone)を添加してスラリー粘度を調整した。
Claims (21)
- ニッケル、コバルト、およびマンガンを含む層状系リチウム金属化合物であって、
アルミニウム、ジルコニウム、およびボロンがドーピングされたものである、リチウム二次電池用正極活物質。 - 前記リチウム金属化合物は、下記化学式1で表される、請求項1に記載のリチウム二次電池用正極活物質:
[化学式1]
LiaNixCoyMnz(M)1−(x+y+z)Ob
前記化学式1で、0.8≦a≦1.3であり、1.8≦b≦2.2であり、0.8≦x≦0.92であり、0<y≦0.15であり、0<z≦0.1であり、0<x+y+z<1であり、ドーピング元素であるMはAl、Zr、およびBを含む。 - 前記正極活物質は、コア部、および前記コア部表面のシェル部を含み、
前記コア部およびシェル部は、前記化学式1内のNi、Co、Mn、およびM元素を含む組成からなる、請求項2に記載のリチウム二次電池用正極活物質。 - 前記コア部は、全体正極活物質直径の100%に対して70乃至80%である、請求項1に記載のリチウム二次電池用正極活物質。
- 前記コア部内のニッケルの含有量は、前記シェル部内のニッケルの含有量より高い、請求項3に記載のリチウム二次電池用正極活物質。
- 前記コア部内のニッケルの含有量分布は均一である、請求項5に記載のリチウム二次電池用正極活物質。
- 前記シェル部内のニッケルの含有量分布は、活物質表面に近いほど減少する濃度勾配を有する、請求項6に記載のリチウム二次電池用正極活物質。
- 前記ドーピング元素であるM中のAlのドーピング比率は、
Ni、Co、Mn、およびMを含む全体金属1モルに対して、
0.0002乃至0.01モルである、請求項2に記載のリチウム二次電池用正極活物質。 - 前記ドーピング元素であるM中のZrのドーピング比率は、
Ni、Co、Mn、およびMを含む全体金属1モルに対して、
0.0015乃至0.005モルである、請求項2に記載のリチウム二次電池用正極活物質。 - 前記ドーピング元素であるM中のBのドーピング比率は、
Ni、Co、Mn、およびMを含む全体金属1モルに対して、
0.001乃至0.01モルである、請求項2に記載のリチウム二次電池用正極活物質。 - 前記正極活物質の結晶サイズ(Crystalline size)は、90nm以上である、請求項1に記載のリチウム二次電池用正極活物質。
- 前記正極活物質のI(003)/I(104)値は、1.2以上である、請求項1に記載のリチウム二次電池用正極活物質。
- 前記正極活物質のR factorは、0.52以下である、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、シェル部表面に位置するコーティング層をさらに含む、請求項1に記載のリチウム二次電池用正極活物質。
- 前記コーティング層は、ボロン、ボロン酸化物、リチウムボロン酸化物またはこれらの組み合わせを含む、請求項14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、大粒径粒子および小粒径粒子が混合されたバイモーダルである、請求項1に記載のリチウム二次電池用正極活物質。
- 前記大粒径粒子のD50が13乃至17μmである、請求項16に記載のリチウム二次電池用正極活物質。
- 前記小粒径粒子のD50が4乃至7μmである、請求項16に記載のリチウム二次電池用正極活物質。
- ニッケル、コバルト、およびマンガンを含む前駆体粒子を準備する段階;
前記前駆体粒子、リチウム原料物質、およびドーピング原料物質を混合して焼成してリチウム金属酸化物を得る段階;
前記リチウム金属酸化物にコーティング原料物質を混合後に焼成してコーティング層を形成させる段階;
を含み、
前記ドーピング原料物質は、Al原料物質、Zr原料物質、およびB原料物質を含む、リチウム二次電池用正極活物質の製造方法。 - 前記前駆体粒子、リチウム原料物質およびドーピング原料物質を混合して焼成してリチウム金属酸化物を得る段階;で、
前記焼成条件は、酸素を流入しながら1次温度および2次温度で連続的に焼成し、
前記1次温度は450乃至550℃であり、前記2次温度は700乃至750℃である、請求項19に記載のリチウム二次電池用正極活物質の製造方法。 - 正極;
負極;および
前記正極と負極との間に位置する電解質を含み、
前記正極は、請求項1に記載の正極活物質を含む、リチウム二次電池。
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JP2023064746A (ja) * | 2021-10-26 | 2023-05-11 | エコプロ ビーエム カンパニー リミテッド | 正極活物質及びこれを含むリチウム二次電池 |
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US11569503B2 (en) | 2016-07-20 | 2023-01-31 | Samsung Sdi Co., Ltd. | Nickel-based active material for lithium secondary battery, method of preparing the same, and lithium secondary battery including positive electrode including the nickel-based active material |
US11302919B2 (en) | 2016-07-20 | 2022-04-12 | Samsung Sdi Co., Ltd. | Nickel-based active material for lithium secondary battery, method of preparing the same, and lithium secondary battery including positive electrode including the nickel-based active material |
PL3333129T3 (pl) | 2016-12-08 | 2021-03-08 | Samsung Sdi Co., Ltd. | Aktywny materiał na bazie niklu do akumulatora litowego, metoda jego przygotowywania oraz akumulator litowy wyposażony w zawierającą ten materiał katodę |
US11456458B2 (en) | 2016-12-08 | 2022-09-27 | Samsung Sdi Co., Ltd. | Nickel-based active material precursor for lithium secondary battery, preparing method thereof, nickel-based active material for lithium secondary battery formed thereof, and lithium secondary battery comprising positive electrode including the nickel-based active material |
US20220320490A1 (en) * | 2019-09-09 | 2022-10-06 | Panasonic Corporation | Positive electrode active material for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery |
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WO2019132332A1 (ko) | 2019-07-04 |
KR102177049B1 (ko) | 2020-11-10 |
EP3734720A4 (en) | 2021-04-14 |
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US20230140577A1 (en) | 2023-05-04 |
JP7008828B2 (ja) | 2022-01-25 |
KR20190078498A (ko) | 2019-07-04 |
CN111771303B (zh) | 2024-03-29 |
CN111771303A (zh) | 2020-10-13 |
US11973221B2 (en) | 2024-04-30 |
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