JP7165120B2 - 電解銅箔、その製造方法、及びリチウムイオン二次電池 - Google Patents
電解銅箔、その製造方法、及びリチウムイオン二次電池 Download PDFInfo
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Description
100 負極
110 電解銅箔
111 生箔層
S1 第1表面
S2 第2表面
SS 光沢表面(S面)
MS 他方の光沢表面(M面)
112a 第1酸化防止処理層
112b 第2酸化防止処理層
120a 第1活性材料層
120b 第2活性材料層
200 正極
300 セパレータ
400 電解槽
R 収容空間
Claims (17)
- 生箔層を含む、電解銅箔であって、
前記生箔層は、第1表面及び前記第1表面に対する第2表面を有し、
熱処理ステップの前後の前記第1表面のX線回折スペクトルにおいて、前記第1表面における(200)結晶面の回折ピーク強度I(200)と前記第1表面における(111)結晶面の回折ピーク強度I(111)の比値(回折ピーク強度I(200)/回折ピーク強度I(111))が0.52から1.29の間であり、
前記熱処理ステップの前後の前記第2表面のX線回折スペクトルにおいて、前記第2表面における(200)結晶面の回折ピーク強度I(200)と前記第2表面における(111)結晶面の回折ピーク強度I(111)の比値(回折ピーク強度I(200)/回折ピーク強度I(111))も0.52から1.29の間であり、
前記熱処理ステップを経過した後、前記電解銅箔の引張り強度は、いずれかの熱処理ステップも経過しない前の引張り強度の65%から95%の間であり、
前記熱処理ステップを経過した後、前記電解銅箔の伸び率は、いずれかの熱処理ステップも経過しない前の伸び率の100%から140%の間であり、
前記熱処理ステップは、前記電解銅箔を130℃から250℃の間の温度環境に放置して0.5時間から1.5時間ベーキングする、電解銅箔。 - 前記第1表面と前記第2表面の間の距離により厚さが定義され、前記厚さが2マイクロメートルから20マイクロメートルの間である、請求項1に記載の電解銅箔。
- 前記電解銅箔がいずれかの熱処理ステップも経過しない前、28kgf/mm2から40kgf/mm2の間の引張り強度、及び7%以上の伸び率を有する、請求項1に記載の電解銅箔。
- 前記電解銅箔が熱処理ステップを経過した後、25kgf/mm2から35kgf/mm2の間の引張り強度、及び9.5%以上の伸び率を有する、請求項3に記載の電解銅箔。
- 前記電解銅箔は、
前記第1表面に設けられた第1酸化防止処理層と、
前記第2表面に設けられた第2酸化防止処理層と、をさらに含み、
前記電解銅箔の総重量を基準に、前記第1酸化防止処理層及び前記第2酸化防止処理層は、いずれも含有量が1重量百万分率(Parts per million、ppm)から1,000重量百万分率の非銅金属元素を含み、
前記非銅金属元素がクロム、亜鉛、ニッケル、モリブデン、マンガン、リン及びそれらの組成物からなる群から選ばれた少なくとも1つの元素である、請求項1に記載の電解銅箔。 - 前記第1表面は、電気めっき過程で回転電気めっきドラム(rotating electrode drum)と接触する表面とさらに限定されると共に、S面(S surface)と定義され、
前記第2表面は、前記S面と対合する表面であることをさらに限定すると共に、M面(M surface)と定義され、
前記S面のX線回折スペクトルにおいて、前記S面の(200)結晶面の回折ピーク強度I(200)と前記S面の(111)結晶面の回折ピーク強度I(111)の比値(回折ピーク強度I(200)/回折ピーク強度I(111))が第1回折ピーク強度比値と定義され、
前記M面のX線回折スペクトルにおいて、前記M面の(200)結晶面の回折ピーク強度I(200)と前記M面の(111)結晶面の回折ピーク強度I(111)の比値(回折ピーク強度I(200)/回折ピーク強度I(111))が第2回折ピーク強度比値と定義され、
前記第1回折ピーク強度比値が前記第2回折ピーク強度比値より小さい、請求項1に記載の電解銅箔。 - 前記第1回折ピーク強度比値と前記第2回折ピーク強度比値との差値の絶対値が0.01以上0.30以下である、請求項6に記載の電解銅箔。
- 前記電解銅箔は複数の結晶粒を有し、いずれかの熱処理ステップも経過しない前、前記結晶粒サイズが20ナノメートルから45ナノメートルの間であり、前記熱処理ステップを経過した後の複数の前記結晶粒の前記結晶粒サイズが、いずれかの熱処理ステップも経過しない前の複数の前記結晶粒の前記結晶粒サイズの90%から130%の間である、請求項1に記載の電解銅箔。
- 第1添加剤、第2添加剤、及び第3添加剤を含む添加剤を、銅電解液の総重量を基準に濃度の総和が12重量百万分率(ppm)以下で含む前記銅電解液を調製するステップと、
前記銅電解液を電解して生箔層を形成する電気めっきステップを実施することと、を含む、電解銅箔の製造方法であって、
前記生箔層は、第1表面及び前記第1表面に対合する第2表面を有し、
前記第1表面のX線回折スペクトルにおいて、前記第1表面における(200)結晶面の回折ピーク強度I(200)と前記第1表面における(111)結晶面の回折ピーク強度I(111)の比値(回折ピーク強度I(200)/回折ピーク強度I(111))が0.52から1.29の間であり、前記第2表面のX線回折スペクトルにおいて、前記第2表面における(200)結晶面の回折ピーク強度I(200)と前記第2表面における(111)結晶面の回折ピーク強度I(111)の比値(回折ピーク強度I(200)/回折ピーク強度I(111))も0.52から1.29の間であり、
前記第1添加剤がその重量平均分子量が1,000から5,000の間であるゼラチン(gelatin)で、前記第2添加剤が0.5重量百万分率(ppm)以下である硫黄原子化合物を含むスルホン酸又はその金属塩類で、且つ前記第3添加物が非イオン水溶性高分子である、電解銅箔の製造方法。 - 前記銅電解液において、前記ゼラチンの濃度と、前記硫黄原子化合物を含むスルホン酸又はその金属塩類の濃度と、前記非イオン水溶性高分子の濃度との総和は、12ppm以下である、請求項9に記載の電解銅箔の製造方法。
- 前記生箔層の前記第1表面に第1酸化防止処理層を形成し、且つ前記生箔層の前記第2表面に第2酸化防止処理層を形成し、それにより、前記生箔層、前記第1酸化防止処理層、及び前記第2酸化防止処理層がともに電解銅箔と形成される酸化防止処理ステップを実施することをさらに含み、
前記電解銅箔の総重量を基準に、前記第1酸化防止処理層及び前記第2酸化防止処理層は、いずれも含有量が1重量百万分率(Parts per million、ppm)から1,000重量百万分率の非銅金属元素を含み、
前記非銅金属元素は、クロム、亜鉛、ニッケル、モリブデン、マンガン、リン及びそれらの組成物からなる群から選ばれた少なくとも1つの元素である、請求項9に記載の電解銅箔の製造方法。 - 電解液を収容するための収容空間を有する電解槽と、
前記電解槽の前記収容空間に設けられた正極と、
前記電解槽の前記収容空間に設けられ、前記正極と間隔をもって設けられ、且つ第1表面及び前記第1表面に対する第2表面を有する電解銅箔を含む負極と、
前記正極及び前記負極の間に設けられたセパレータと、を含み、
熱処理ステップの前後の前記電解銅箔の前記第1表面のX線回折スペクトルにおいて、前記第1表面における(200)結晶面の回折ピーク強度I(200)と前記第1表面における(111)結晶面の回折ピーク強度I(111)の比値(回折ピーク強度I(200)/回折ピーク強度I(111))が0.52から1.29の間であり、
前記熱処理ステップの前後の前記電解銅箔の前記第2表面のX線回折スペクトルにおいて、前記第2表面における(200)結晶面の回折ピーク強度I(200)と前記第2表面における(111)結晶面の回折ピーク強度I(111)の比値(回折ピーク強度I(200)/回折ピーク強度I(111))も0.52から1.29の間であり、
前記熱処理ステップを経過した後、前記電解銅箔の引張り強度は、いずれかの熱処理ステップも経過しない前の引張り強度の65%から95%の間であり、
前記熱処理ステップを経過した後、前記電解銅箔の伸び率は、いずれかの熱処理ステップも経過しない前の伸び率の100%から140%の間であり、
前記熱処理ステップは、前記電解銅箔を130℃から250℃の間の温度環境に放置して0.5時間から1.5時間ベーキングする、リチウムイオン二次電池。 - 前記第1表面と前記第2表面の間の距離により厚さが定義され、前記厚さは、2マイクロメートルから20マイクロメートルの間である、請求項12に記載のリチウムイオン二次電池。
- 前記電解銅箔がいずれかの熱処理ステップも経過しない前、前記電解銅箔が28kgf/mm2から40kgf/mm2の引張り強度、及び7%以上の伸び率を有する、請求項12に記載のリチウムイオン二次電池。
- 前記電解銅箔が熱処理ステップを経過した後、前記電解銅箔が25kgf/mm2から35kgf/mm2の引張り強度、及び9.5%以上の伸び率を有する、請求項12に記載のリチウムイオン二次電池。
- 前記電解銅箔は、
前記第1表面に設けられた第1酸化防止処理層と、
前記第2表面に設けられた第2酸化防止処理層と、
をさらに含み、
前記電解銅箔の総重量を基準に、前記第1酸化防止処理層及び前記第2酸化防止処理層はいずれも含有量が1重量百万分率(Parts per million、ppm)から1,000重量百万分率の非銅金属元素を含み、且つ前記非銅金属元素がクロム、亜鉛、ニッケル、モリブデン、マンガン、リン及びそれらの組成物からなる群から選ばれた少なくとも1つの元素である、請求項12に記載のリチウムイオン二次電池。 - 前記電解銅箔は複数の結晶粒を有し、いずれかの熱処理ステップも経過しない前の前記結晶粒サイズが20ナノメートルから45ナノメートルの間であり、前記熱処理ステップを経過した後、複数の前記結晶粒の前記結晶粒サイズが、いずれかの前記熱処理ステップも経過しない前の複数の前記結晶粒の前記結晶粒サイズの90%から130%の間である、請求項12に記載のリチウムイオン二次電池。
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