JP6161015B2 - リチウム二次電池用負極材、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材、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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- JP6161015B2 JP6161015B2 JP2015515964A JP2015515964A JP6161015B2 JP 6161015 B2 JP6161015 B2 JP 6161015B2 JP 2015515964 A JP2015515964 A JP 2015515964A JP 2015515964 A JP2015515964 A JP 2015515964A JP 6161015 B2 JP6161015 B2 JP 6161015B2
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- carbon
- negative electrode
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- silicon
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- 229910052744 lithium Inorganic materials 0.000 title claims description 32
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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Description
実施例1
平均粒径(D50)が約20μm程度の黒鉛粒子上に金(Au)を配置させ、黒鉛と金をバッチタイプ(batch type)反応器に入れた。前記反応器の温度を約400℃に維持したあと、キャリアガスとしてアルゴン(Ar)を利用して反応ガスであるSiH4を流しながら蒸気−液体−固体(VLS)反応を起こした。これにより、黒鉛粒子上に直径が10から100nmで、長さが2μmであるシリコンナノワイヤを成長させた。反応時間によってシリコンナノワイヤの重量を調節することができ、本実施例では黒鉛とシリコンナノワイヤの重量比は92重量%:8重量%であった。
シリコンナノワイヤが成長された黒鉛粒子上に炭素コーティング層を形成させないことを除いては、実施例1と同様の方法で負極材を製造した。黒鉛とシリコンナノワイヤの重量比は92重量%:8重量%であった。
実施例2
前記実施例1で製造された負極材、バインダーとしてSBR(Styrene-Butadiene Rubber)、増粘剤としてCMC(Carboxy Methyl Cellulose)及び導電材としてアセチレンブラックを95:2:2:1の重量比で混合し、これらを溶媒である水(H2O)とともに混合して均一な負極スラリーを製造した。製造された負極スラリーを銅集電体の一面に65μmの厚さにコーティングし、乾燥及び圧延したあと、必要な大きさにパンチング(punching)して負極を製造した。
比較例1で製造された負極材を用いたことを除いては、実施例2と同様の方法でコイン型のリチウム二次電池を製造した。
<SEM顕微鏡写真:炭素コーティング層形成の確認>
前記比較例1及び実施例1で製造された負極材を、それぞれSEM顕微鏡写真でシリコンナノワイヤが成長された程度を確認しており、その結果を図2及び3に示した。
<SEM顕微鏡写真:炭素系粒子及びシリコンナノワイヤの物理的結合力の確認>
前記比較例1及び実施例1で製造された負極材を、水、エタノール、トルエンに1g/mLで希釈して60℃で12時間の間撹拌したあと、それぞれの溶媒にシリコンナノワイヤが残った程度をSEM顕微鏡写真で確認しており、その結果を図4及び図5に示した。
<サイクル特性>
実施例2及び比較例2のリチウム二次電池に対し、充放電器(WBCS 3000、WON A TECH)を利用して充放電特性を評価した。
Claims (12)
- 炭素系粒子と、
前記炭素系粒子上に成長されたシリコンナノワイヤと、
前記炭素系粒子及び前記シリコンナノワイヤの表面上に形成された炭素コーティング層とを含み、
前記炭素系粒子の平均粒径(D50)は、10μmから30μmであり、
前記シリコンナノワイヤは、10nmから100nmの直径及び100nmから5μmの長さを有し、
前記シリコンの含量は、シリコンナノワイヤが成長された炭素系粒子の全体重量に対し5重量%から30重量%であり、
前記炭素コーティング層の厚さは5nmから50nmであり、
前記炭素コーティング層は、炭素系粒子及び前記シリコンナノワイヤの表面を全部覆う負極材。 - 前記炭素系粒子は、炭素系粉末、炭素ブラック、天然黒鉛及び人造黒鉛からなる群から選ばれるいずれか又はこれらのうち2種以上の混合物を含む請求項1に記載の負極材。
- 前記炭素系粒子の比表面積(BET)は2.0m2/gから5.0m2/gであり、圧縮密度は12mpaから16mpaの圧力下で1.5g/ccから1.85g/ccである請求項1または2に記載の負極材。
- 炭素系粒子上にシリコン原料及び触媒金属を利用して炭素系粒子上にシリコンナノワイヤを成長させるステップと、
前記シリコンナノワイヤ、及び前記シリコンナノワイヤが成長された炭素系粒子の表面を全部覆うように炭素コーティング層を形成するステップとを含み、
前記炭素コーティング層は、非晶質炭素前駆体を利用してシリコンナノワイヤが成長された炭素系粒子をコーティングし熱処理して形成され、
前記コーティングは、有機溶媒に浸漬された前記非晶質炭素前駆体を利用した湿式コーティング法により行われ、
前記非晶質炭素前駆体は、重量平均分子量が500から800である石炭系ピッチ又は石油系ピッチであり、
前記有機溶媒は、エタノール、トルエン、メタノール、ヘキサン、アセトン、テトラヒドロフラン、ピリジン、キノリン及びベンゾキノンからなる群から選ばれるいずれか、又はこれらのうち2種以上の混合物であり、
前記熱処理は、非活性雰囲気下で行われる負極材の製造方法。 - 前記シリコンナノワイヤの成長は、蒸気−液体−固体(VLS;Vapor phase-Liquid phase-Solid phase)法、固体−液体−固体(SLS;Solid-Liquid-Solid)法、有機金属化学気相蒸着(MOCVD : Metal Organic Chemical Vapor Deposition)法及びMBE(Molecular Beam Epitaxy)法からなる群から選ばれる方法で行われる請求項4に記載の負極材の製造方法。
- 前記シリコン原料は、SiCl4、SiH4又はこれらの混合物を含む請求項4または5に記載の負極材の製造方法。
- 前記触媒金属は、金(Au)、鉄(Fe)、銀(Ag)及びニッケル(Ni)からなる群から選ばれるいずれか、又はこれらのうち2種以上の混合金属を含む請求項4から6の何れか一項に記載の負極材の製造方法。
- 前記湿式コーティング法は、前記非晶質炭素前駆体が希釈された有機溶媒に、前記シリコンナノワイヤが成長された炭素系粒子を浸漬して行われる請求項4から7の何れか一項に記載の負極材の製造方法。
- 前記シリコンナノワイヤが成長された炭素系粒子と前記非晶質炭素前駆体の混合比は90から99重量部:1から10重量部である請求項4から8の何れか一項に記載の負極材の製造方法。
- 前記熱処理は、300℃から1500℃の温度範囲で行われる請求項4から9の何れか一項に記載の負極材の製造方法。
- 集電体、及び前記集電体の少なくとも一面に形成された請求項1から3の何れか一項に記載の負極材を含む負極。
- 正極、請求項11に記載の負極及び前記正極と負極との間に介在されたセパレーターを含むリチウム二次電池。
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