JP2021527921A - リチウム二次電池用正極活物質及びリチウム二次電池 - Google Patents
リチウム二次電池用正極活物質及びリチウム二次電池 Download PDFInfo
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- JP2021527921A JP2021527921A JP2020566271A JP2020566271A JP2021527921A JP 2021527921 A JP2021527921 A JP 2021527921A JP 2020566271 A JP2020566271 A JP 2020566271A JP 2020566271 A JP2020566271 A JP 2020566271A JP 2021527921 A JP2021527921 A JP 2021527921A
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- Prior art keywords
- positive electrode
- transition metal
- lithium
- metal oxide
- lithium secondary
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 128
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- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 68
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000011229 interlayer Substances 0.000 claims abstract description 56
- 229910006715 Li—O Inorganic materials 0.000 claims abstract description 55
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- 239000003792 electrolyte Substances 0.000 claims abstract description 21
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 16
- 150000003624 transition metals Chemical class 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 11
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- 239000000126 substance Substances 0.000 claims description 17
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- 229910052749 magnesium Inorganic materials 0.000 claims description 10
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Abstract
Description
本出願は、2018年6月20日に出願された韓国特許出願第10−2018−0071055号に基づいた優先権の利益を主張し、当該韓国特許出願の文献に開示された全ての内容は本明細書の一部として含まれる。
Lix[NiaCobMncMd]O2
本発明による正極は正極活物質層を含み、前記正極活物質層は、正極活物質で層状構造を有し、且つ遷移金属全体のうちニッケルの含有量が85atm%以上であるリチウム複合遷移金属酸化物の粉末を含む。
Lix[NiaCobMncMd]O2
本発明において、前記負極は、通常、リチウム二次電池で用いられるものであれば、特に制限なく使用可能であり、例えば、負極集電体及び前記負極集電体上に位置する負極活物質層を含むものであってよい。
前記分離膜は、負極と正極の間に介在し、正極及び負極を分離してリチウムイオンの移動通路を提供するものであって、通常、リチウム二次電池で分離膜に用いられるものであれば特に制限なく使用可能であり、特に電解質のイオン移動に対して低抵抗でありながら電解液含湿能に優れたものが好ましい。具体的には、多孔性高分子フィルム、例えば、エチレン単独重合体、プロピレン単独重合体、エチレン/ブテン共重合体、エチレン/ヘキセン共重合体及びエチレン/メタクリレート共重合体などのようなポリオレフィン系高分子で製造した多孔性高分子フィルムまたはこれらの2層以上の積層構造体が用いられてよい。また、通常の多孔性不織布、例えば、高融点のガラス繊維、ポリエチレンテレフタレート繊維などからなる不織布が用いられてもよい。また、耐熱性または機械的強度の確保のためにセラミックス成分または高分子物質が含まれたコーティングされた分離膜が用いられてもよく、選択的に単層または多層構造で用いられてよい。
前記電解質としては、リチウム二次電池に使用可能な有機系液体電解質、無機系液体電解質、固体高分子電解質、ゲル型高分子電解質、固体無機電解質、溶融型無機電解質などが用いられてよく、特に限定されない。
Ni0.88Co0.09Mn0.03(OH)2とLiOH、ZrO2、及びAl(OH)3を乾式混合し、760℃で12時間の間焼成し、Al及びZrがドーピングされたリチウム複合遷移金属酸化物の粉末を製造した。
Ni0.88Co0.09Mn0.03(OH)2とLiOH、ZrO2、WO3、及びAl(OH)3を乾式混合し、740℃で12時間の間焼成し、Al、Zr及びWがドーピングされたリチウム複合遷移金属酸化物を製造した。
Ni0.90Co0.08Mn0.02(OH)2とLiOH、TiO2、及びWO3を乾式混合し、760℃で12時間の間焼成し、Ti及びWがドーピングされたリチウム複合遷移金属酸化物を製造した。
Ni0.90Co0.08Mn0.02(OH)2とLiOH、ZrO2、WO3、及びAl(OH)3を乾式混合し、760℃で12時間の間焼成し、Al、Zr及びWがドーピングされたリチウム複合遷移金属酸化物を製造した。
前記製造例1〜4により製造されたそれぞれのリチウム複合遷移金属酸化物と、カーボンブラック導電材及びPVDFバインダーをN‐メチルピロリドン溶媒中において重量比で96.5:1.5:2.0の比率で混合して正極合剤を製造し、これをアルミニウム集電体の片面に塗布した後、130℃で乾燥し、圧延して正極を製造した。
正極活物質として製造例1により製造されたリチウム複合遷移金属酸化物、カーボンブラック導電材及びPVDFバインダーをN‐メチルピロリドン溶媒中において重量比で96.5:1.5:2.0の比率で混合して正極合剤を製造し、これをアルミニウム集電体の片面に塗布した後、130℃で乾燥し、圧延して正極を製造した。
正極活物質として製造例2により製造されたリチウム複合遷移金属酸化物を用いた点を除いては、実施例1と同一の方法でリチウム二次電池を製造した。
正極活物質として製造例3により製造されたリチウム複合遷移金属酸化物を用いた点を除いては、実施例1と同一の方法でリチウム二次電池を製造した。
正極活物質として製造例4により製造されたリチウム複合遷移金属酸化物を用いた点を除いては、実施例1と同一の方法でリチウム二次電池を製造した。
実施例1〜3及び比較例1のリチウム二次電池の容量特性を次の方法で測定した。
実施例1〜3及び比較例1のリチウム二次電池の高温寿命特性を次の方法で測定した。
Claims (8)
- 正極、負極、前記正極と前記負極との間に介在する分離膜、及び電解質を含むリチウム二次電池であって、
前記正極は、正極活物質で層状構造を有し且つ遷移金属全体のうちニッケルの含有量が85atm%以上であるリチウム複合遷移金属酸化物の粉末を含み、
前記リチウム複合遷移金属酸化物の粉末はSOC58%から72%充電区間におけるLi‐O層間距離の変化率が3%以下である、リチウム二次電池。 - 前記リチウム複合遷移金属酸化物の粉末はSOC58%から72%充電区間におけるLi‐O層間距離の変化率が1%以下である、請求項1に記載のリチウム二次電池。
- 前記リチウム複合遷移金属酸化物の粉末はSOC100%で充電した状態におけるLi‐O層間距離がSOC0%の状態におけるLi‐O層間距離以上である、請求項1又は2に記載のリチウム二次電池。
- 前記リチウム複合遷移金属酸化物は、下記化学式1で表され、
[化学式1]
Lix[NiaCobMncMd]O2
前記化学式1中、
前記Mは、W、Cu、Fe、V、Cr、Ti、Zr、Zn、Al、In、Ta、Y、La、Sr、Ga、Sc、Gd、Sm、Ca、Ce、Nb、Mg、B、及びMoよりなる群から選択される1種以上の元素であり、
0.9≦x≦1.2、0.85≦a≦0.99、0<b<0.15、0<c<0.15、0<d<0.15である、請求項1から3のいずれか一項に記載のリチウム二次電池。 - 前記Mは、W、Zr、Al、Ti及びMgよりなる群から選択される2種以上の元素を含む、請求項4に記載のリチウム二次電池。
- 前記Mは、Wと、Zr、Al、Ti及びMgよりなる群から選択された1種以上の元素を含む、請求項4に記載のリチウム二次電池。
- 前記リチウム複合遷移金属酸化物は、その表面にAl、Ti、W、B、F、P、Mg、Ni、Co、Fe、Cr、V、Cu、Ca、Zn、Zr、Nb、Mo、Sr、Sb、Bi、Si、及びSよりなる群から選択された1種以上の元素を含むコーティング層を含む、請求項1から6のいずれか一項に記載のリチウム二次電池。
- 層状構造を有し且つ遷移金属全体のうちニッケルの含有量が85atm%以上であるリチウム複合遷移金属酸化物の粉末を含むリチウム二次電池用正極活物質であって、
前記リチウム複合遷移金属酸化物の粉末は、SOC58%から72%充電区間におけるLi‐O層間距離の変化率が3%以下である、正極活物質。
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JP2020149954A (ja) * | 2019-03-15 | 2020-09-17 | 株式会社豊田自動織機 | 層状岩塩構造を示し、リチウム、ニッケル、コバルト、タングステン、アルミニウム、ジルコニウム及び酸素を含有する正極活物質、並びに、その製造方法 |
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US20210226206A1 (en) | 2021-07-22 |
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KR20190143292A (ko) | 2019-12-30 |
EP3800713A4 (en) | 2021-06-23 |
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