JP6972324B2 - リチウム二次電池用負極、この製造方法及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負極、この製造方法及びこれを含むリチウム二次電池 Download PDFInfo
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- JP6972324B2 JP6972324B2 JP2020516465A JP2020516465A JP6972324B2 JP 6972324 B2 JP6972324 B2 JP 6972324B2 JP 2020516465 A JP2020516465 A JP 2020516465A JP 2020516465 A JP2020516465 A JP 2020516465A JP 6972324 B2 JP6972324 B2 JP 6972324B2
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- Prior art keywords
- negative electrode
- lithium
- secondary battery
- active material
- lithium secondary
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 127
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 239000007773 negative electrode material Substances 0.000 claims description 63
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 52
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- 239000010439 graphite Substances 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 34
- 239000010409 thin film Substances 0.000 claims description 32
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- 238000007740 vapor deposition Methods 0.000 claims description 19
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- 229910052814 silicon oxide Inorganic materials 0.000 claims description 15
- 239000005278 LISON - lithium–sulfur oxynitride Substances 0.000 claims description 14
- 239000008151 electrolyte solution Substances 0.000 claims description 13
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 12
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- 230000008569 process Effects 0.000 claims description 10
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- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
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Description
負極集電体;及び前記負極集電体上に形成された負極活物質層;を含むリチウム二次電池用負極であって、前記負極活物質層はグラファイト及びシリコンオキシドを含み、前記負極活物質層内にリチウム(Li)が注入されたリチウム二次電池用負極を提供する。
本発明による負極活物質層112は、グラファイト及びシリコンオキシドを含み、前記負極活物質層内にリチウム(Li)が注入されてもよい。
本発明による負極集電体111は、電池に化学的変化を引き起こさずに高い導電性を有するものであれば特に制限せず、銅、アルミニウム、ステンレススチール、亜鉛、チタン、銀、パラジウム、ニッケル、鉄、クロム、これらの合金からなる群から選択されてもよい。前記ステンレススチールは、カーボン、ニッケル、チタンまたは銀で表面処理されてもよく、前記合金としては、アルミニウム−カドミウム合金を使用することができ、その他にも焼成炭素、導電材で表面処理された非伝導性高分子、または伝導性高分子などを使用することもできる。一般的に負極集電体としては銅薄板を適用する。また、その形態は表面に微小凹凸が形成された/未形成されたフィルム、シート、ホイル、ネット、多孔質体、発泡体、不織布体など多様な形態が使われてもよい。
図2は本発明の別の実施例による負極110を示す図面である。
図3は本発明のまた別の実施例による負極110を示す図面である。
図1は本発明の一実施例による負極110を示す図面である。
本発明によるリチウム二次電池は、前述した負極の構造及び特性を除いた他の構成に対しては、通常の技術者が実施する公知の技術を通じて製造することが可能である。
負極の製造
100μm厚さの銅ホイルを負極集電体で準備した。以後、水を溶媒にして、グラファイトとシリコンオキシド(SiO)を70:30重量%で混合した活物質と、導電材(SuperP)、バインダー(SBR BM480B)、添加剤(CMC Daicel2200)を97.5:0.7:0.9:0.9(活物質:導電材:バインダー:添加剤)で混合した活物質スラリーを製造した後、これを負極集電体上にウェットコーティング(Wet coating)で塗布した後で乾燥し、150μm厚さの負極活物質層を製造した。
Li密度:0.534g/cm3
単位体積当たり容量:2068mAh/cm3
負極活物質層上に、リチウム金属を2μmの厚さで熱蒸着した後、10−6Torrの工程圧力で640℃の蒸着温度で1時間行ったことを除いては、前記実施例1と同様の方法で負極を製造した。前記負極活物質層に注入されたリチウムの量を換算してみれば、1cm2の面積にLiを厚さ2μmで蒸着した時、0.4136mAhが発現され、電荷量は1.484Cで、注入されたリチウムのモル濃度は1.54×10 −5 mol/cm 2 であった。具体的な算式は次のとおりである。
Li密度:0.534g/cm3
単位体積当たり容量:4136mAh/cm3
負極活物質層上に、リチウム金属を3μmの厚さで熱蒸着した後、10−6Torrの工程圧力で640℃の蒸着温度で1時間行ったことを除いて、前記実施例1と同様の方法で負極を製造した。前記負極活物質層に注入されたリチウムの量を換算してみれば、1cm2の面積にLiを厚さ3μmで蒸着した時、0.6204mAhが発現され、電荷量は2.226Cで、注入されたリチウムのモル濃度は2.31×10 −5 mol/cm 2 であった。具体的な算式は次のとおりである。
Li密度:0.534g/cm3
単位体積当たり容量:6204mAh/cm3
リチウムを熱蒸着しないことを除いて、前記実施例1と同様の方法で負極を製造した。
100μm厚さのアルミニウムホイル上に、Ni:Mn:Co=8:1:1組成のリチウム金属酸化膜を形成して正極を製造した。以後、前記で製造された負極を適用した後、正極及び負極の間にポリオレフィン分離膜を介在した後、1M LiPF6塩(salt)が溶解された電解液を注入して電池を製造した。前記電解液の中で溶媒の組成はEC:PC:DMC=5:3:2であった。
実施例1ないし実施例3及び比較例1の負極を使用して製造したリチウム二次電池に対して、それぞれの物性を測定した。この時、厚さが変化する場合、セルを分解して実測する破壊検査であるため、初期活性化工程を進めた後で1回行い、初期活性化容量基準のエネルギー密度(Energy Density)を算出した。その結果を下記表1及び図4ないし図5に示す。
前記実施例1ないし実施例3及び比較例1の負極を使用して製造したリチウム二次電池を対象にして、充電電圧を4.2Vカット(cut)、レート(Rate)を0.5Cにし、放電電圧を2.5Vカット(cut)、レート(Rate)を0.5Cにして充/放電過程で充電容量と放電容量を測定し、サイクル(Cycle)による変化は図6にサイクル能力データ(Cycle Capability Data)で示す。
111:集電体
112:負極活物質層
113:リチウム薄膜層
114:薄膜層
Claims (14)
- 負極集電体;及び
前記負極集電体上に形成された負極活物質層;を含むリチウム二次電池用負極であって、
前記負極活物質層はグラファイト及びシリコンオキシドを含み、
前記負極活物質層内にリチウム(Li)が注入され、
前記リチウムが注入されたグラファイトはLi x C 6 (0<x≦1)であり、
前記リチウムが注入されたシリコンオキシドはLi x Si y O(0<y/x≦4.4)である、リチウム二次電池用負極。 - 前記リチウム(Li)がグラファイト及びシリコンオキシド内に注入された、請求項1に記載のリチウム二次電池用負極。
- 前記リチウム(Li)が1×10 −6 ないし1×10 −4 mol/cm2で注入された、請求項2に記載のリチウム二次電池用負極。
- 前記リチウム(Li)が5×10 −6 ないし5×10 −5 mol/cm2で注入された、請求項2に記載のリチウム二次電池用負極。
- 前記リチウム(Li)が1×10 −5 ないし2×10 −5 mol/cm2で注入された、請求項2に記載のリチウム二次電池用負極。
- 前記リチウム(Li)が注入されたグラファイトとリチウム(Li)が注入されたシリコンオキシドは、6:4ないし8:2の重量比で含まれる、請求項2から5のいずれか一項に記載のリチウム二次電池用負極。
- 前記負極活物質層上に、フッ化リチウム(LiF)、アルミナ(Al2O3)、グラファイト(Graphite)、LiPON(リチウムリン酸窒化物(Lithium Phosphorus Oxynitride))及びLiSON(リチウム硫黄酸窒化物(Lithium Sulfur Oxynitride))からなる群から選択されるいずれか一つ以上の物質を含む薄膜層をさらに含む、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用負極。
- 前記薄膜層は0.1ないし10μmの厚さで形成される、請求項7に記載のリチウム二次電池用負極。
- (a)負極集電体上にグラファイト及びシリコンオキシド(SiO)を含む活物質スラリーを塗布して負極活物質層を形成する段階;及び
(b)前記負極活物質層にリチウム(Li)を熱蒸着(Thermal Evaporation)またはスパッタリング(Sputtering)して負極活物質層にリチウムを注入する段階;を含み、
前記(b)段階は、負極活物質層にリチウム(Li)を0.1ないし10μmで蒸着させた後、10 −7 ないし10 −5 Torrの工程圧力で600ないし700℃の蒸着温度で30分ないし2時間熱蒸着させる、リチウム二次電池用負極の製造方法。 - 前記(b)段階後、(c)フッ化リチウム(LiF)、アルミナ(Al2O3)、グラファイト(Graphite)、LiPON(リチウムリン酸窒化物(Lithium Phosphorus Oxynitride))及びLiSON(リチウム硫黄酸窒化物(Lithium Sulfur Oxynitride))からなる群から選択されるいずれか一つ以上の物質を熱蒸着(Thermal Evaporation)またはスパッタリング(Sputtering)して薄膜層を形成する段階をさらに含む、請求項9に記載のリチウム二次電池用負極の製造方法。
- 前記(b)段階は、負極活物質層にリチウム(Li)を0.5ないし5μmで蒸着させる、請求項9又は10に記載のリチウム二次電池用負極の製造方法。
- 前記(b)段階は、負極活物質層にリチウム(Li)を1ないし3μmで蒸着させる、請求項9又は10に記載のリチウム二次電池用負極の製造方法。
- 前記(c)段階は、負極活物質層に前記物質を10−7ないし10−5Torrのベース圧力(base pressure)で、1m Torrないし100m Torrの工程圧力(working pressure)でスパッタリング(Sputtering)する、請求項10に記載のリチウム二次電池用負極の製造方法。
- 正極、負極、両電極の間に介在された分離膜及び電解液を含み、
前記負極は、請求項1ないし請求項8のいずれか一項に記載の負極である、リチウム二次電池。
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