JP2017538858A - 電解銅箔、それを含む電極、それを含む二次電池、及びその製造方法 - Google Patents
電解銅箔、それを含む電極、それを含む二次電池、及びその製造方法 Download PDFInfo
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 160
- 239000011889 copper foil Substances 0.000 title claims abstract description 115
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 229910052802 copper Inorganic materials 0.000 claims description 45
- 239000010949 copper Substances 0.000 claims description 45
- 239000010410 layer Substances 0.000 claims description 26
- 239000011149 active material Substances 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- 239000011241 protective layer Substances 0.000 claims description 24
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 21
- 230000003449 preventive effect Effects 0.000 claims description 21
- 239000008151 electrolyte solution Substances 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 238000004070 electrodeposition Methods 0.000 claims description 11
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 8
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 8
- 238000005520 cutting process Methods 0.000 claims description 8
- 238000007667 floating Methods 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 6
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 229910052793 cadmium Inorganic materials 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 6
- 229910052732 germanium Inorganic materials 0.000 claims description 6
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 239000006259 organic additive Substances 0.000 claims description 6
- -1 silane compound Chemical class 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 4
- 239000012964 benzotriazole Substances 0.000 claims description 4
- 229910001431 copper ion Inorganic materials 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 4
- 229910001416 lithium ion Inorganic materials 0.000 claims description 4
- 108010010803 Gelatin Proteins 0.000 claims description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- 238000005868 electrolysis reaction Methods 0.000 claims description 3
- 229920000159 gelatin Polymers 0.000 claims description 3
- 239000008273 gelatin Substances 0.000 claims description 3
- 235000019322 gelatine Nutrition 0.000 claims description 3
- 235000011852 gelatine desserts Nutrition 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 150000004767 nitrides Chemical class 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000002347 injection Methods 0.000 claims 1
- 239000007924 injection Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 38
- 230000037303 wrinkles Effects 0.000 abstract description 11
- 239000010408 film Substances 0.000 description 34
- 239000007773 negative electrode material Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 238000005507 spraying Methods 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910009369 Zn Mg Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
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- H—ELECTRICITY
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- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/24—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
-
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
-
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
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- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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Abstract
Description
式:RD=[|R1−R2|/(R1,R2)max]×100
電解槽内の電解液中に互いに離隔して配置された陽極板と回転陰極ドラムを通電させることによって、前記回転陰極ドラム上に銅膜を形成した。前記電解液は、85g/Lの銅イオン、75g/Lの硫酸、20ppmの塩素イオン、及び有機添加剤を含んでいる。前記有機添加剤としてはゼラチン、ヒドロキシエチルセルロース(HEC)、有機硫化物、及び有機窒化物が使用された。前記銅膜111形成ステップにおいて、前記電解液は約55℃に維持され、前記電解槽内に供給される前記電解液の流量は40m3/hourであった。
前記第1陽極板によって提供される電流密度が70A/dm2であること以外は、実施例1と同様の方法で電解銅箔を製造した。
前記第1陽極板と第2陽極板との間に第3陽極板がさらに提供され、前記第3陽極板によって提供される電流密度が55A/dm2であること以外は、実施例1と同様の方法で電解銅箔を製造した。
前記第1及び第2陽極板によって50A/dm2の同じ電流密度が提供される以外は、実施例1と同様の方法で電解銅箔を製造した。
前記第1及び第2陽極板によって50A/dm2の同じ電流密度が提供され、酸化クロム溶液の噴射過程を省略した以外は、実施例1と同様の方法で電解銅箔を製造した。
酸化クロム溶液の噴射過程を省略した以外は、実施例1と同様の方法で電解銅箔を製造した。
AAS(Atomic Absorption Spectrometry)分析を通じて、電解銅箔の第1面(銅膜のシャイニー面に隣接する面)及びその反対側の第2面のクロム電着量をそれぞれ測定した。
JIS B 0601−1994の規定に準拠して、接触式表面粗さ測定機を用いて電解銅箔の第1面(銅膜のシャイニー面に隣接する面)及びその反対側の第2面の10点平均粗さ(RzJIS)をそれぞれ測定した。
式:RD=[|R1−R2|/(R1,R2)max]×100
Claims (15)
- 第1面及び前記第1面の反対側の第2面を有する電解銅箔(electrolytic copper foil)であって、
前記第1面側の第1保護層と、
前記第2面側の第2保護層と、
前記第1保護層と前記第2保護層との間の銅膜(copper film)とを含み、
前記電解銅箔は、30mm以下の縦方向の浮き及び25mm以下の横方向の浮きを有し、前記横方向の浮きは前記縦方向の浮きの8.5倍以下である、電解銅箔:
ここで、前記縦方向の浮き及び前記横方向の浮きは、前記電解銅箔の中心部を5cm×5cmのX状の切断ラインに沿って切断するものの、前記電解銅箔に形成されている転写跡と平行な縦方向と35°〜55°の角をなす第1方向、及び前記第1方向と垂直な第2方向に切断することによって、前記縦方向に沿って並んで配置される一対の第1セグメント、及び前記縦方向と垂直な横方向に沿って並んで配置される一対の第2セグメントを形成する場合、前記第1セグメントの前記第1面又は第2面の方向への浮きの程度のうち相対的に大きい値、及び前記第2セグメントの前記第1面又は第2面の方向への浮きの程度のうち相対的に大きい値をそれぞれ意味する。 - 前記第1及び第2保護層は、防錆物質(anticorrosion material)が前記銅膜上に電着されることによってそれぞれ形成され、
前記第1保護層と第2保護層との前記防錆物質の電着量の差は2.5ppm/m2以下である、請求項1に記載の電解銅箔。 - 前記防錆物質は、クロム酸塩、ベンゾトリアゾール、酸化クロム及びシラン化合物のうち少なくとも1つを含む、請求項2に記載の電解銅箔。
- 前記電解銅箔は4〜35μmの厚さを有する、請求項1に記載の電解銅箔。
- 前記第1面及び第2面は、3.5μm以下の10点平均粗さ(ten−point mean roughness:RzJIS)を有し、
次式によって算出される前記第1面と第2面との10点平均粗さの偏差が70%以下である、請求項1に記載の電解銅箔:
式:RD=[|R1−R2|/(R1,R2)max]×100
ここで、R1は、前記第1面の10点平均粗さであり、R2は、前記第2面の10点平均粗さであり、RDは、前記第1面と第2面との10点平均粗さの偏差であり、|R1−R2|は、前記第1面と第2面との10点平均粗さの差であり、(R1,R2)maxは、前記第1面及び第2面の10点平均粗さのうち相対的に大きい10点平均粗さである。 - 請求項1に記載の電解銅箔と、
前記電解銅箔上の活物質層とを含み、
前記活物質層は、炭素、Si、Ge、Sn、Li、Zn、Mg、Cd、Ce、Ni又はFeの金属、前記金属を含む合金、前記金属の酸化物、及び前記金属と炭素の複合体からなる群から選択される1つ以上の活物質を含む、二次電池用電極。 - 正極(cathode)と、
負極(anode)と、
前記正極と負極との間でリチウムイオンが移動できる環境を提供する電解質(electrolyte)と、
前記正極と前記負極を電気的に絶縁させる分離膜(separator)とを含み、
前記負極は、
請求項1に記載の電解銅箔と、
前記電解銅箔上の活物質層とを含み、
前記活物質層は、炭素、Si、Ge、Sn、Li、Zn、Mg、Cd、Ce、Ni又はFeの金属、前記金属を含む合金、前記金属の酸化物、及び前記金属と炭素の複合体からなる群から選択される1つ以上の活物質を含む、二次電池。 - 電解槽内の電解液中に互いに離隔して配置された陽極板と回転陰極ドラムを通電させることによって、前記回転陰極ドラム上に銅膜を形成する銅膜形成ステップと、
前記銅膜を防錆液(anticorrosion solution)に浸漬させる浸漬ステップとを含み、
前記陽極板は、互いに電気的に絶縁された第1陽極板及び第2陽極板を含み、
前記銅膜形成ステップは、前記第1陽極板と前記回転陰極ドラムとの間の通電によってシード層を形成し、次いで、前記第2陽極板と前記回転陰極ドラムとの間の通電によって前記シード層を成長させることによって行われ、
前記第1陽極板によって提供される電流密度は、前記第2陽極板によって提供される電流密度の1.5倍以上である、電解銅箔の製造方法。 - 前記陽極板は、前記第1陽極板と第2陽極板との間に第3陽極板をさらに含み、
前記第3陽極板によって提供される電流密度は、前記第1陽極板によって提供される電流密度よりも小さく、前記第2陽極板によって提供される電流密度よりも大きい、請求項8に記載の電解銅箔の製造方法。 - 前記陽極板によって提供される電流密度は40〜70A/dm2である、請求項8又は9に記載の電解銅箔の製造方法。
- 前記防錆液に浸漬された前記銅膜を前記防錆液から引き出す引き出しステップをさらに含み、
前記浸漬ステップ及び前記引き出しステップが行われるとき、前記銅膜は、前記防錆液中に配置されたガイドロール(guide roll)によって案内される、請求項8に記載の電解銅箔の製造方法。 - 前記銅膜が前記防錆液から引き出された後、前記浸漬ステップ中に前記ガイドロールと接触した前記銅膜の面上に防錆液を噴射する防錆液噴射ステップをさらに含む、請求項11に記載の電解銅箔の製造方法。
- 前記電解液は、50〜100g/Lの銅イオン、50〜150g/Lの硫酸、50ppm以下の塩素イオン、及び有機添加剤を含む、請求項8に記載の電解銅箔の製造方法。
- 前記有機添加剤は、ゼラチン、ヒドロキシエチルセルロース(HEC)、有機硫化物、有機窒化物、チオ尿素(thiourea)系化合物、またはこれらのうちの2つ以上の混合物である、請求項13に記載の電解銅箔の製造方法。
- 前記銅膜形成ステップ中に前記電解槽内に供給される前記電解液の流量は40〜46m3/hourである、請求項8に記載の電解銅箔の製造方法。
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