JP7368616B2 - リチウム-硫黄電池用負極及びこれを含むリチウム-硫黄電池 - Google Patents
リチウム-硫黄電池用負極及びこれを含むリチウム-硫黄電池 Download PDFInfo
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Description
[実施例1]
厚さが20μmの銅集電体を1035℃の温度で20分間300sccmのアルゴンガスと50sccmの水素ガスを流して酸化された銅薄膜の表面を還元させ、銅表面の予備-ファセッティングを遂行した。その後、1035℃で20sccmメタンガスをさらに注入し、ロールツーロールの移動速度は6m/hrに設定して化学気相蒸着を遂行することで両表面に厚さ1.0nmのグラフェンを含む保護層が形成された銅集電体を製造した。
実施例1で得た保護層が形成された銅集電体の一面に45μm厚さのリチウム金属ホイルを載せて、ロールプレス(roll press)で圧搾して負極を製造した。
実施例1で得た保護層が形成された銅集電体の両面に同一厚さのリチウム金属ホイルを圧搾した負極を使用してバイセル(Bi-cell)が5個積層されたポーチセルに製造したことを除いては、前記実施例2と同様の方法でポーチ型リチウム-硫黄電池を製造した。
化学気相蒸着時、メタンガスの注入速度を5sccmに、ロールツーロール移動速度は1.5m/hrにそれぞれ変更したことを除いては、前記実施例1と同様の方法で両表面に厚さが1.5nmのグラフェンを含む保護層が形成された銅集電体を製造した。
実施例1の代わりに実施例4の保護層が形成された銅集電体を使用したことを除いては、前記実施例2と同様の方法でコイン型リチウム-硫黄電池を製造した。
化学気相蒸着時、水素ガスの注入速度を25sccmに変更したことを除いては、前記実施例1と同様の方法で両表面に厚さが35nmのグラフェンを含む保護層が形成された銅集電体を製造した。
実施例1の代わりに実施例6の保護層が形成された銅集電体を使用したことを除いては、前記実施例2と同様の方法でコイン型リチウム-硫黄電池を製造した。
化学気相蒸着時、水素ガスの注入速度を35sccmに変更したことを除いては、前記実施例1と同様の方法で両表面に厚さが20nmのグラフェンを含む保護層が形成された銅集電体を製造した。
実施例1の代わりに実施例8の保護層が形成された銅集電体を使用したことを除いては、前記実施例2と同様の方法でコイン型リチウム-硫黄電池を製造した。
保護層を形成していない厚さ20μmの銅薄膜を銅集電体で製造した。
実施例1の代わりに比較例1の銅集電体を使用したことを除いては、前記実施例2と同様の方法でコイン型リチウム-硫黄電池を製造した。
実施例1の代わりに比較例1の銅集電体を使用したことを除いては、前記実施例3と同様の方法でポーチ型リチウム-硫黄電池を製造した。
剥離グラフェンパウダー(G3社製品)95重量%、スチレンブタジエンゴム/カルボキシメチルセルロース(SBR/CMC 7:3)5重量%を混合してスラリー組成物を製造した。
実施例1の代わりに比較例4の銅集電体を使用したことを除いては、前記実施例2と同様の方法でコイン型リチウム-硫黄電池を製造した。
化学気相蒸着時、水素ガスの注入速度を5sccmに変更したことを除いては、前記実施例1と同様の方法で両表面に厚さが100nmのグラフェンを含む保護層が形成された銅集電体を製造した。
実施例1の代わりに比較例6の保護層が形成された銅集電体を使用したことを除いては、前記実施例2と同様の方法でコイン型リチウム-硫黄電池を製造した。
実施例1及び比較例1で製造した保護層が形成された銅集電体に対して走査電子顕微鏡(scanning electron microscope;SEM)で表面を観察した。走査電子顕微鏡ではゼオル(JEOL)社のJSM7610Fを利用した。この時、得られた結果は図1及び2に示す。
(1)保護層の耐酸化性及びグラフェン結晶粒の大きさ
実施例1及び4で製造した保護層が形成された銅集電体を200℃で6時間人為的な熱酸化反応を遂行した後、X-線光電子分光分析装置を利用して銅酸化度を測定した。
実施例1、実施例4、実施例6、比較例1及び比較例4によって製造された保護層のグラフェンに対してラマン分光器(Raman-XploRA、HORIBA Scientific)を利用してラマン分光分析を実施した。また、実施例6で製造した保護層が形成された銅集電体に対して走査電子顕微鏡(scanning electron microscope;SEM)で断面を観察した。走査電子顕微鏡ではゼオル(JEOL)社のJSM7610Fを利用した。この時、得られた結果は表3及び図4に示す。
実施例2、実施例3、実施例5、実施例7、実施例9、比較例2、比較例3、比較例5及び比較例7で製造したリチウム-硫黄電池に対して寿命特性を評価した。
Claims (12)
- 負極集電体、及び
前記負極集電体の少なくとも一面に位置し、グラフェンを含む保護層を含み、
前記グラフェンはラマンスペクトルでのDピークとGピークの割合が0.01ないし0.6である、リチウム-硫黄電池用負極。 - 前記保護層は単一層グラフェンまたは多層グラフェンを含む、請求項1に記載のリチウム-硫黄電池用負極。
- 前記多層グラフェンは2ないし100層である、請求項2に記載のリチウム-硫黄電池用負極。
- 前記グラフェンはラマンスペクトルでの2DピークとGピークの割合が0.2ないし2.0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-硫黄電池用負極。
- 前記保護層は厚さが0.1ないし50nmである、請求項1から4のいずれか一項に記載のリチウム-硫黄電池用負極。
- 前記負極集電体は、ニッケル、銅、ステンレススチール、チタン、バナジウム、クロム、マンガン、鉄、コバルト、亜鉛、モリブデン、タングステン、銀、金、ルテニウム、白金、イリジウム、アルミニウム、スズ、ビスマス及びアンチモンからなる群から選択される1種以上を含む、請求項1から5のいずれか一項に記載のリチウム-硫黄電池用負極。
- 前記負極集電体は、フィルム、シート、ホイル、メッシュ、ネット、多孔質体、発泡体または不織布体の形態を含む、請求項1から6のいずれか一項に記載のリチウム-硫黄電池用負極。
- 前記リチウム-硫黄電池用負極は前記保護層上に負極活物質層をさらに含む、請求項1から7のいずれか一項に記載のリチウム-硫黄電池用負極。
- 前記負極活物質層はリチウム金属またはリチウム合金を含む、請求項8に記載のリチウム-硫黄電池用負極。
- 前記負極活物質層はリチウム金属薄膜を含む、請求項8に記載のリチウム-硫黄電池用負極。
- 正極活物質を含む正極、
請求項1から10のいずれか一項に記載のリチウム-硫黄電池用負極、及び
電解質を含むリチウム-硫黄電池。 - 前記正極活物質は、無機硫黄、Li2Sn(n≧1)、ジスルフィド化合物、有機硫黄化合物及び炭素-硫黄ポリマー((C2Sx)n、x=2.5ないし50、n≧2)からなる群から選択される1種以上を含む、請求項11に記載のリチウム-硫黄電池。
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KR102172024B1 (ko) * | 2013-07-16 | 2020-10-30 | 삼성에스디아이 주식회사 | 집전체 구조 및 이를 채용한 전극과 리튬 전지 |
KR20150113661A (ko) * | 2014-03-31 | 2015-10-08 | 주식회사 엘지화학 | 전극 집전체 및 전극의 제조방법 |
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KR101879502B1 (ko) * | 2015-09-11 | 2018-07-18 | 한양대학교 산학협력단 | 계면층이 도입된 이차전지용 음극 및 이의 제조방법 |
KR101930130B1 (ko) | 2016-06-10 | 2018-12-17 | 한양대학교 산학협력단 | 질소가 도핑된 탄소를 함유하는 양극 활물질층 및 보호막을 구비하는 금속-황 전지용 양극, 이의 제조방법 |
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AU2019384179A1 (en) | 2018-11-23 | 2021-07-08 | Icad, Inc | System and method for assessing breast cancer risk using imagery |
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- 2021-07-23 CN CN202180005927.2A patent/CN114556612A/zh active Pending
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JP2013140770A (ja) | 2011-12-28 | 2013-07-18 | Qinghua Univ | 集電体、それを利用した電気化学電池用電極及び電気化学電池 |
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