JP7078741B2 - リチウム金属電池用負極及びそれを含むリチウム金属電池 - Google Patents
リチウム金属電池用負極及びそれを含むリチウム金属電池 Download PDFInfo
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Description
グラフェンとSiO2とを、グラフェンの含量がSiO2の重量を基準として42.5重量%となるように定量して混合し、それを約105℃で1200分間反応して、グラフェンボールを製造した。
製造例1で製造されたグラフェンボールを、静電気を用いてPETフィルム上に分散させた後、圧縮加圧により、リチウム金属負極上に転写させ、負極を製造した。
負極として、前記実施例1の負極の代わりに、グラフェンボールの転写過程を経ていないリチウム金属を使用したことを除いては、実施例1と同様な方法により、コインセルを製造した。
実施例1及び比較例1で製造されたコインセルに対して、0.1mV/sのスキャン速度で循環電圧電流法測定を実施した。
実施例1及び比較例1によって製造されたコインセルに対して、それぞれ25℃で、0.8mAの電流で、電圧が4.40V(vs.Li)に至るまで定電流充電し、次いで、定電圧モードで4.40Vを維持しながら、0.5Vまたは8mAhの電流でカットオフした。10分間休止期間を有した後、放電時に電圧が3.0V(vs.Li)に至るまで、0.8mAの定電流で放電した(化成段階、最初のサイクル)。
THF溶媒と、製造例1で製造されたグラフェンボールとを90:10の重量比で混合して、グラフェンボールスラリーを製造した。前記グラフェンボールスラリーをリチウム金属負極の表面に30μmの厚さに塗布して、負極を製造した。
前記グラフェンボールスラリーを60μmの厚さに塗布したことを除いては、実施例2と同様な方法により、リチウム金属電池を製造した。
前記グラフェンボールスラリーの代わりに、カーボン層を30μmの厚さにリチウム金属負極上に圧延して塗布し、負極を製造したことを除いては、実施例2と同様な方法により、リチウム金属電池を製造した。
製造例1で製造されたグラフェンボール0.05g、LiFSI 0.02g、N-メチルピロリドン4g及びPVDF 0.1gを混合した後、100分間ソニケーションを経て、グラフェンボールスラリーを製造した。このように製造されたグラフェンボールスラリーを、リチウム金属負極上に約5μmの厚さに塗布した後、60℃で一晩乾燥させ、負極を製造した。
前記グラフェンボールスラリーの代わりに、ポリスチレン・ポリイソプレン共重合体を、5μmの厚さにリチウム金属負極に塗布して、負極を製造したことを除いては、実施例2と同様な方法により、リチウム金属電池を製造した。
実施例2ないし5によって製造されたリチウム金属電池(フルセル)、及び比較例2によって製造されたリチウム金属電池(フルセル)に対して、25℃で、0.7C rateの電流で、電圧が4.40V(vs.Li)に至るまで定電流充電し、次いで、定電圧モードで4.40Vを維持しながら、0.05C rateの電流でカットオフした。10分間休止期間を有した後、放電時に電圧が3.0V(vs.Li)に至るまで、0.5C rateの定電流で放電した(化成段階、最初のサイクル)。そのような充放電過程を二回さらに実施し、化成過程を完了した。
Claims (14)
- リチウム金属負極を含む第1負極と、
前記第1負極上に配置され、炭素系物質を含むコーティング層を含む第2負極と、を含み、
前記炭素系物質は、グラフェン及びシリコン系物質を含む球状のグラフェンボールであり、
前記シリコン系物質は、SiOx(1<x<3)であることを特徴とするリチウム金属電池用負極。 - 前記グラフェンボールは、シリコン系物質を、グラフェンボールの総重量を基準として、50ないし80重量%の量で含むことを特徴とする請求項1に記載のリチウム金属電池用負極。
- 前記グラフェンボールの比表面積は、80ないし120m2/gであることを特徴とする請求項1に記載のリチウム金属電池用負極。
- 前記グラフェンボールの常温(25℃)での電気伝導度は、10ないし50S/cmであることを特徴とする請求項1に記載のリチウム金属電池用負極。
- 前記コーティング層は、ハードカーボンまたはソフトカーボンを含むカーボン層であることを特徴とする請求項1に記載のリチウム金属電池用負極。
- 前記コーティング層は、高分子バインダ及びリチウム塩のうち一つ以上をさらに含むことを特徴とする請求項1に記載のリチウム金属電池用負極。
- 前記高分子バインダは、フッ化ビニリデン/ヘキサフルオロプロピレンコポリマー、ポリフッ化ビニリデン(PVDF)、ポリアクリロニトリル、ポリメチルメタクリレート、ポリテトラフルオロエチレン及びスチレンブタジエンゴム系ポリマーのうち選択された一つ以上であることを特徴とする請求項6に記載のリチウム金属電池用負極。
- 前記リチウム塩は、LiDFOB,LiFSI,LiSCN,LiN(CN)2,LiClO4,LiBF4,LiAsF6,LiPF6,LiCF3SO3,LiC(CF3SO2)3,LiN(SO2C2F5)2,LiN(SO2CF3)2,LiN(SO2F)2,LiSbF6、LiPF3(CF2CF3)3,LiPF3(CF3)3及びLiB(C2O4)2のうち選択された一つ以上であることを特徴とする請求項6に記載のリチウム金属電池用負極。
- 前記コーティング層の厚さは、2ないし100μmであることを特徴とする請求項1に記載のリチウム金属電池用負極。
- 前記第2負極上に、固体電解質界面(Solid electrolyte interface: SEI)被膜をさらに含むことを特徴とする請求項1に記載のリチウム金属電池用負極。
- 正極と、
請求項1ないし請求項10のいずれか一項に記載のリチウム金属電池用負極と、
前記正極と負極との間に介在される電解質と、を含むことを特徴とするリチウム金属電池。 - 前記正極は、下記化学式1で表示される正極活物質を含み、
[化1]LiCo1-xMxO2
前記式中、
Mは、Ni,Mn,Al,Cu,Fe,Mg,Cr,Zn,B及びGaからなる群から選択された一つ以上であり、
0.5<x<1である、
ことを特徴とする請求項11に記載のリチウム金属電池。 - 前記電解質は、リチウム塩及び有機溶媒を含む液体電解質であることを特徴とする請求項11に記載のリチウム金属電池。
- 前記有機溶媒は、カーボネート系化合物またはエーテル系化合物であることを特徴とする請求項13に記載のリチウム金属電池。
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KR10-2017-0165353 | 2017-12-04 | ||
PCT/KR2018/012345 WO2019112167A1 (ko) | 2017-12-04 | 2018-10-18 | 리튬금속전지용 음극 및 이를 포함한 리튬금속전지 |
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US20210091413A1 (en) * | 2019-09-25 | 2021-03-25 | The Regents Of The University Of California | Scalable 3d lithium metal anode |
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EP3723169A1 (en) | 2020-10-14 |
US20240145703A1 (en) | 2024-05-02 |
US11575130B2 (en) | 2023-02-07 |
CN111433946A (zh) | 2020-07-17 |
US20230062428A1 (en) | 2023-03-02 |
KR20190065817A (ko) | 2019-06-12 |
US20200365892A1 (en) | 2020-11-19 |
JP2021506090A (ja) | 2021-02-18 |
CN111433946B (zh) | 2023-11-07 |
KR102490867B1 (ko) | 2023-01-20 |
US11876223B2 (en) | 2024-01-16 |
WO2019112167A1 (ko) | 2019-06-13 |
EP3723169A4 (en) | 2021-08-25 |
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