JP2018109226A - Electrolytic copper foil having optimum peak roughness, electrode comprising the same, secondary battery comprising the same, and method for producing the same - Google Patents

Electrolytic copper foil having optimum peak roughness, electrode comprising the same, secondary battery comprising the same, and method for producing the same Download PDF

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JP2018109226A
JP2018109226A JP2017242428A JP2017242428A JP2018109226A JP 2018109226 A JP2018109226 A JP 2018109226A JP 2017242428 A JP2017242428 A JP 2017242428A JP 2017242428 A JP2017242428 A JP 2017242428A JP 2018109226 A JP2018109226 A JP 2018109226A
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copper foil
electrolytic copper
secondary battery
electrolytic
active material
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JP6527219B2 (en
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スン ミン キム
Sun Min Kim
スン ミン キム
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LS Mtron Ltd
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    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/10—Other heavy metals
    • C23G1/103—Other heavy metals copper or alloys 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
    • 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
    • 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
    • C25D5/003—Electroplating using gases, e.g. pressure influence
    • 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
    • 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
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

PROBLEM TO BE SOLVED: To provide an electrolytic copper foil having a peak roughness (Rp) optimized for enhancing capacity retention of a secondary battery, an electrode comprising the same, a secondary battery comprising the same, and a method for producing the same.SOLUTION: An electrolytic foil 110 is provided which comprises a first surface and a second surface opposite to the first surface. The first surface and the second surface each have a peak roughness (Rp) of 0.36 to 1.69 μm, in which the difference between a peak roughness (Rp) on the first surface and a peak roughness (Rp) on the second surface is 0.6 μm or less. In the electrolytic foil 110, the first surface has a first protecting layer 112a, and the second surface has a second protecting layer 112b; the protecting layers 112a, 112b each have Cr; its adhesion amounts range from 0.5 to 5.5 mg/m; and its difference is 2.5 mg/mor less. The electrolytic foil 110 has a thickness of 4 to 20 μm and a yield strength of 21 to 58 kgf/mmat room temperature of 25±15°C.SELECTED DRAWING: Figure 1

Description

本発明は二次電池の容量維持率（ｃａｐａｃｉｔｙ ｍａｉｎｔｅｎａｎｃｅ）を向上させるために最適化したピーク粗さ（ｐｅａｋ ｒｏｕｇｈｎｅｓｓ：Ｒｐ）を有する電解銅箔、それを含む電極、それを含む二次電池、およびその製造方法に関するものである。   The present invention relates to an electrolytic copper foil having a peak roughness (Rp) optimized to improve the capacity maintenance of a secondary battery, an electrode including the same, a secondary battery including the same, and It relates to the manufacturing method.

二次電池は、電気エネルギーを化学エネルギーの形態に変えて貯蔵してから電気が必要な時に前記化学エネルギーを電気エネルギーに変換させることによって電気を発生させるエネルギー変換機器の一種であって、携帯電話、ノートパソコンなどのような携帯用の家電はもちろん、電気自動車のエネルギー源として利用されている。   A secondary battery is a kind of energy conversion device that generates electricity by converting electrical energy into chemical energy form and storing it, and then converting the chemical energy into electrical energy when electricity is needed. It is used as an energy source for electric vehicles as well as portable home appliances such as notebook computers.

使い捨ての一次電池と比べ、経済的かつ環境的に利点を有している二次電池としては、鉛蓄電池、ニッケルカドミウム二次電池、ニッケル水素二次電池、リチウム二次電池などがある。   Secondary batteries having economic and environmental advantages over disposable primary batteries include lead storage batteries, nickel cadmium secondary batteries, nickel hydride secondary batteries, lithium secondary batteries, and the like.

リチウム二次電池は、他の二次電池と比べて大きさおよび重量対比相対的に多くのエネルギーを貯蔵することができる。したがって、携帯性および移動性が重要な情報通信機器分野の場合、リチウム二次電池が好まれており、ハイブリッド自動車および電気自動車のエネルギー貯蔵装置にもその応用範囲が拡大している。   Lithium secondary batteries can store a relatively large amount of energy relative to size and weight compared to other secondary batteries. Therefore, in the field of information communication equipment where portability and mobility are important, lithium secondary batteries are preferred, and the application range is expanding to energy storage devices of hybrid vehicles and electric vehicles.

リチウム二次電池は、充電と放電を一つの周期として繰り返し使われる。完全に充電したリチウム二次電池で、ある機器を稼動させる時、前記機器の稼動時間を増やすためには前記リチウムイオン二次電池が高い充電／放電容量を有さなければならない。したがって、リチウム二次電池の充電／放電容量に対する需要者の日々高まる期待値（ｎｅｅｄｓ）を満足させるための研究が持続的に要求されている。   Lithium secondary batteries are repeatedly used with charging and discharging as one cycle. When operating a device with a fully charged lithium secondary battery, the lithium ion secondary battery must have a high charge / discharge capacity in order to increase the operating time of the device. Accordingly, there is a continuing need for research to satisfy the daily needs of consumers for the charge / discharge capacity of lithium secondary batteries.

リチウム二次電池の容量を増加させるための一つの方法として、炭素活物質にＳｉまたはＳｎが添加された複合活物質を、二次電池の陰極製造時に電解銅箔上に塗布する活物質として使うことが提案された。しかし、このような複合活物質はリチウム二次電池が充電または放電される時に発生する熱によって急激に、そして激しく膨張して電解銅箔の破断をもたらす。リチウム二次電池の充放電が繰り返されるにつれて陰極活物質の収縮および膨張が交互に発生し、これは前記銅箔と陰極活物質間の分離を誘発してリチウム二次電池の充放電容量維持率を低下させる。特に、銅箔と陰極活物質の間の接着強度が弱いほどリチウム二次電池の充放電容量維持率が深刻に低下する。   As one method for increasing the capacity of a lithium secondary battery, a composite active material in which Si or Sn is added to a carbon active material is used as an active material to be coated on an electrolytic copper foil when manufacturing a secondary battery cathode. It was proposed. However, such a composite active material expands rapidly and violently due to heat generated when the lithium secondary battery is charged or discharged, resulting in breakage of the electrolytic copper foil. As the charging / discharging of the lithium secondary battery is repeated, the cathode active material contracts and expands alternately, which induces separation between the copper foil and the cathode active material, thereby maintaining the charge / discharge capacity maintenance rate of the lithium secondary battery. Reduce. In particular, the lower the adhesive strength between the copper foil and the cathode active material, the more seriously decreases the charge / discharge capacity retention rate of the lithium secondary battery.

充電／放電サイクルが繰り返されるにつれて二次電池の充電／放電容量が急激に減少するのであれば（すなわち、容量維持率が低いまたは寿命が短いのであれば）、消費者は二次電池を頻繁に取り替える必要があり、それによって消費者に不便を与え、および資源の浪費をもたらしてしまうであろう。   If the charge / discharge capacity of the secondary battery decreases rapidly as the charge / discharge cycle is repeated (ie, if the capacity maintenance rate is low or the life is short), the consumer frequently uses the secondary battery. It will need to be replaced, which will inconvenience consumers and waste resources.

リチウム二次電池の容量を増加させるためには、陰極製造に使われる電解銅箔の厚さが薄くなければならない。しかし、厚さが薄いほど電解銅箔はカール（ｃｕｒｌ）またはシワ（ｗｒｉｎｋｌｅ）に、さらに脆弱となる。このような電解銅箔のカールまたはシワは作業性を低下させるだけでなく、活物質のコーティング自体を不可能にする。   In order to increase the capacity of the lithium secondary battery, the thickness of the electrolytic copper foil used for manufacturing the cathode must be thin. However, the thinner the thickness, the more vulnerable the electrolytic copper foil to curls or wrinkles. Such curling or wrinkling of the electrolytic copper foil not only reduces workability but also makes the active material coating itself impossible.

したがって、本発明は、前記のような関連技術の制限および短所に起因した問題点を防止できる電解銅箔、それを含む電極、それを含む二次電池、およびその製造方法に関するものである。   Therefore, the present invention relates to an electrolytic copper foil, an electrode including the same, a secondary battery including the same, and a method for manufacturing the same, which can prevent the problems caused by the limitations and disadvantages of the related art as described above.

本発明の一観点は、高い容量維持率を有する二次電池を担保できる電解銅箔を提供することである。   One aspect of the present invention is to provide an electrolytic copper foil that can secure a secondary battery having a high capacity retention rate.

本発明の他の観点は、高い容量維持率を有する二次電池を担保できる電極を提供することである。   Another aspect of the present invention is to provide an electrode that can secure a secondary battery having a high capacity retention rate.

本発明のさらに他の観点は、高い容量維持率を有する二次電池を提供することである。   Still another aspect of the present invention is to provide a secondary battery having a high capacity retention rate.

本発明のさらに他の観点は、高い容量維持率を有する二次電池を担保できる銅箔を製造する方法を提供することである。   Still another aspect of the present invention is to provide a method for producing a copper foil that can secure a secondary battery having a high capacity retention rate.

前述した本発明の観点の他にも、本発明の他の特徴および利点が以下で説明されるか、そのような説明から本発明が属する技術分野で通常の知識を有する者に明確に理解されるはずである。   In addition to the aspects of the present invention described above, other features and advantages of the present invention are described below or are clearly understood by those having ordinary skill in the art to which the present invention belongs. Should be.

前記のような本発明の一観点により、第１面とその反対側の第２面を有する電解銅箔であって、前記第１面に向かうマット面（ｍａｔｔｅ ｓｕｒｆａｃｅ）および前記第２面に向かうシャイニー面（ｓｈｉｎｙ ｓｕｒｆａｃｅ）を含む銅層；前記マット面上の第１保護層；および前記シャイニー面上の第２保護層を含み、前記第１および第２面のそれぞれは０．３６〜１．６９μｍのピーク粗さ（ｐｅａｋ ｒｏｕｇｈｎｅｓｓ：Ｒｐ）を有し、前記第１面のピーク粗さと前記第２面のピーク粗さの差は０．６μｍ以下であることを特徴とする、電解銅箔が提供される。   According to one aspect of the present invention as described above, an electrolytic copper foil having a first surface and a second surface opposite to the first surface, the mat surface facing the first surface and the second surface. A copper layer including a shiny surface; a first protective layer on the mat surface; and a second protective layer on the shiny surface, each of the first and second surfaces being 0.36-1. An electrolytic copper foil having a peak roughness (Rp) of 69 μm, wherein a difference between a peak roughness of the first surface and a peak roughness of the second surface is 0.6 μm or less. Provided.

前記第１および第２保護層のそれぞれはクロム（Ｃｒ）を含むことができ、前記第１および第２面のそれぞれにおけるクロム（Ｃｒ）付着量は０．５〜５．５ｍｇ／ｍ２であり得る。 Each of the first and second protective layers may include chromium (Cr), and a chromium (Cr) deposition amount on each of the first and second surfaces is 0.5 to 5.5 mg / m 2 . obtain.

前記第１面でのクロム（Ｃｒ）付着量と前記第２面でのクロム（Ｃｒ）付着量の差は２．５ｍｇ／ｍ２以下であり得る。 The difference between the chromium (Cr) deposition amount on the first surface and the chromium (Cr) deposition amount on the second surface may be 2.5 mg / m 2 or less.

前記第１および第２面のそれぞれの表面粗さＲｚは２．５μｍ以下であり得る。   The surface roughness Rz of each of the first and second surfaces may be 2.5 μm or less.

前記電解銅箔は２５±１５℃の常温で２１〜５８ｋｇｆ／ｍｍ２の降伏強度を有することができる。 The electrolytic copper foil may have a yield strength of 21 to 58 kgf / mm 2 at a room temperature of 25 ± 15 ° C.

前記電解銅箔は４〜３０μｍの厚さを有することができる。   The electrolytic copper foil may have a thickness of 4 to 30 μm.

本発明の他の観点により、第１面とその反対側の第２面を有する電解銅箔；および前記第１面上の第１活物質層を含み、前記電解銅箔は、前記第１面に向かうマット面および前記第２面に向かうシャイニー面を含む銅層；前記マット面上の第１保護層；および前記シャイニー面上の第２保護層を含み、前記第１および第２面のそれぞれは０．３６〜１．６９μｍのピーク粗さ（ｐｅａｋ ｒｏｕｇｈｎｅｓｓ：Ｒｐ）を有し、前記第１面のピーク粗さと前記第２面のピーク粗さの差は０．６μｍ以下であることを特徴とする、二次電池用電極が提供される。   According to another aspect of the present invention, an electrolytic copper foil having a first surface and a second surface opposite to the first surface; and a first active material layer on the first surface, wherein the electrolytic copper foil includes the first surface A copper layer including a matte surface facing the surface and a shiny surface facing the second surface; a first protective layer on the mat surface; and a second protective layer on the shiny surface, each of the first and second surfaces Has a peak roughness (Rp) of 0.36 to 1.69 μm, and the difference between the peak roughness of the first surface and the peak roughness of the second surface is 0.6 μm or less. An electrode for a secondary battery is provided.

前記第１および第２保護層のそれぞれはクロム（Ｃｒ）を含むことができ、前記第１および第２面のそれぞれにおけるクロム（Ｃｒ）付着量は０．５〜５．５ｍｇ／ｍ２であり得、前記第１面でのクロム（Ｃｒ）付着量と前記第２面でのクロム（Ｃｒ）付着量の差は２．５ｍｇ／ｍ２以下であり得る。 Each of the first and second protective layers may include chromium (Cr), and a chromium (Cr) deposition amount on each of the first and second surfaces is 0.5 to 5.5 mg / m 2 . The difference between the chromium (Cr) deposition amount on the first surface and the chromium (Cr) deposition amount on the second surface may be 2.5 mg / m 2 or less.

前記電解銅箔は２５±１５℃の常温で２１〜５８ｋｇｆ／ｍｍ２の降伏強度を有することができる。 The electrolytic copper foil may have a yield strength of 21 to 58 kgf / mm 2 at a room temperature of 25 ± 15 ° C.

前記二次電池用電極は、前記第２面上の第２活物質層をさらに含むことができ、前記第１および第２活物質層は、互いに独立して、炭素；Ｓｉ、Ｇｅ、Ｓｎ、Ｌｉ、Ｚｎ、Ｍｇ、Ｃｄ、Ｃｅ、ＮｉまたはＦｅの金属；前記金属を含む合金；前記金属の酸化物；および前記金属と炭素の複合体からなる群から選択される一つ以上の活物質をそれぞれ含むことができる。   The electrode for a secondary battery may further include a second active material layer on the second surface, and the first and second active material layers may be formed of carbon; Si, Ge, Sn, One or more active materials selected from the group consisting of a metal of Li, Zn, Mg, Cd, Ce, Ni or Fe; an alloy containing the metal; an oxide of the metal; and a composite of the metal and carbon. Each can be included.

本発明のさらに他の観点により、陽極（ｃａｔｈｏｄｅ）；前記二次電池用電極で構成された陰極（ａｎｏｄｅ）；前記陽極と陰極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）；および前記陽極と前記陰極を電気的に絶縁させる分離膜（ｓｅｐａｒａｔｏｒ）を含むことを特徴とする、二次電池が提供される。   According to still another aspect of the present invention, an anode; a cathode composed of the secondary battery electrode; an electrolyte providing an environment in which lithium ions can move between the anode and the cathode; A secondary battery comprising a separator for electrically insulating the anode and the cathode is provided.

本発明のさらに他の観点により、銅層を形成する段階；および前記銅層上に保護層を形成する段階を含み、前記銅層形成段階は、５０〜１００ｇ／Ｌの銅イオン、５０〜１５０ｇ／Ｌの硫酸、３〜１２ｐｐｍのビス（３−スルホプロピル）ジスルフィド［ｂｉｓ−（３−ｓｕｌｆｏｐｒｏｐｙｌ）ｄｉｓｕｌｆｉｄｅ：ＳＰＳ］、および５０ｐｐｍ以下の塩素を含む電解液を準備する段階；および前記電解液内に互いに離隔して配置された電極板および回転電極ドラムを４０〜８０Ａ／ｄｍ２の電流密度で通電させることによって電気メッキを行う段階を含み、前記電気メッキが行われる間、前記電解液内の全炭素量（Ｔｏｔａｌ Ｃａｒｂｏｎ：ＴＣ）は０．２５ｇ／Ｌ以下に維持され、前記電解液内のスカンジウム（Ｓｃ）およびイットリウム（Ｙ）の総濃度は３５０ｍｇ／Ｌ以下に維持され、前記回転電極ドラムの表面は＃８００〜＃１５００の粒度（Ｇｒｉｔ）を有する研磨ブラシで研磨されたことを特徴とする、電解銅箔の製造方法が提供される。 According to still another aspect of the present invention, the method includes forming a copper layer; and forming a protective layer on the copper layer, wherein the copper layer forming step includes 50 to 100 g / L of copper ions, 50 to 150 g. Providing an electrolyte comprising / L sulfuric acid, 3-12 ppm bis (3-sulfopropyl) disulfide (bis- (3-sulfopropyl) disulphide: SPS), and 50 ppm or less chlorine; and in the electrolyte Electroplating by energizing an electrode plate and a rotating electrode drum that are spaced apart from each other at a current density of 40 to 80 A / dm 2 , and during the electroplating, The amount of carbon (TC) is maintained at 0.25 g / L or less, and scandium (Sc) and it The total concentration of um (Y) is maintained at 350 mg / L or less, and the surface of the rotating electrode drum is polished with a polishing brush having a grain size (Grit) of # 800 to # 1500. A manufacturing method is provided.

前記電解液準備段階は、銅ワイヤーを６００〜９００℃で３０〜６０分の間熱処理する段階；前記熱処理された銅ワイヤーを酸洗する段階；および前記酸洗した銅ワイヤーを硫酸に投入する段階を含むことができる。   The electrolytic solution preparing step includes a step of heat-treating the copper wire at 600 to 900 ° C. for 30 to 60 minutes; a step of pickling the heat-treated copper wire; and a step of adding the pickled copper wire to sulfuric acid Can be included.

前記銅層形成段階は、前記電気メッキが行われる間過酸化水素および空気を前記電解液に投入する段階をさらに含むことができる。   The copper layer forming step may further include a step of introducing hydrogen peroxide and air into the electrolyte while the electroplating is performed.

前記電解液はヒドロキシエチルセルロース（ＨＥＣ）、有機硫化物、有機窒化物、グリコール（ｇｌｙｃｏｌ）系高分子、およびチオ尿素（ｔｈｉｏｕｒｅａ）系化合物から構成されたグループから選択される少なくとも一つの有機添加剤をさらに含むことができる。   The electrolyte includes at least one organic additive selected from the group consisting of hydroxyethyl cellulose (HEC), organic sulfides, organic nitrides, glycol polymers, and thiourea compounds. Further can be included.

前記保護層形成段階は０．５〜１．５ｇ／ＬのＣｒを含む防錆液内に前記銅層を浸漬させる段階を含むことができる。   The protective layer forming step may include a step of immersing the copper layer in a rust preventive solution containing 0.5 to 1.5 g / L of Cr.

前記のような本発明に対する一般的な叙述は本発明を例示するか説明するためのものに過ぎず、本発明の権利範囲を制限しない。   The foregoing general description of the present invention is merely intended to illustrate or explain the present invention and does not limit the scope of the present invention.

本発明によると、充放電サイクルの繰り返しにもかかわらず、高い充電／放電容量を長期間維持できる長寿名の二次電池が製造され得る。したがって、二次電池の頻繁な取り替えによる電子製品消費者の不便および資源の浪費を最小化することができる。   According to the present invention, a longevity secondary battery capable of maintaining a high charge / discharge capacity for a long period of time despite repeated charge / discharge cycles can be manufactured. Therefore, the inconvenience of consumers of electronic products and waste of resources due to frequent replacement of the secondary battery can be minimized.

添付された図面は、本発明の理解を助け、本明細書の一部を構成するためのものである。以下、本発明の実施例を例示し、発明の詳細な説明と共に本発明の原理を説明する。
本発明の一実施例に係る二次電池用電極の断面図である。 ＪＩＳＢ０６０１（２００１）規格に沿って得られた表面粗さプロファイルを例示した図面である。 実施例１の電解銅箔を利用して製造された二次電池の充／放電実験後の陰極の状態を示している写真である。 比較例１の電解銅箔を利用して製造された二次電池の充／放電実験後の陰極の状態を示している写真である。 The accompanying drawings are intended to assist the understanding of the present invention and to constitute a part of this specification. Examples of the present invention will be illustrated below, and the principle of the present invention will be described together with the detailed description of the invention.
It is sectional drawing of the electrode for secondary batteries which concerns on one Example of this invention. It is drawing which illustrated the surface roughness profile obtained along JISB0601 (2001) specification. It is the photograph which shows the state of the cathode after the charging / discharging experiment of the secondary battery manufactured using the electrolytic copper foil of Example 1. FIG. It is the photograph which shows the state of the cathode after the charging / discharging experiment of the secondary battery manufactured using the electrolytic copper foil of the comparative example 1.

以下、添付された図面を参照して本発明の実施例を詳細に説明する。   Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

本発明の技術的思想および範囲を逸脱しない範囲内で本発明の多様な変更および変形が可能であることは当業者に自明であろう。したがって、本発明は特許請求の範囲に記載された発明およびその均等物の範囲内に入る変更および変形をすべて含む。   It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention. Accordingly, this invention includes all modifications and variations that fall within the scope of the claimed invention and its equivalents.

リチウムイオン二次電池は、陽極（ｃａｔｈｏｄｅ）、陰極（ａｎｏｄｅ）、前記陽極と陰極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）、および一つの電極で発生した電子が二次電池の内部を通じて他の電極に移動することによって無駄に消耗することを防止するために、前記陽極と陰極を電気的に絶縁させる分離膜（ｓｅｐａｒａｔｏｒ）を含む。   A lithium ion secondary battery includes an anode, a cathode, an electrolyte that provides an environment in which lithium ions can move between the anode and the cathode, and electrons generated in one electrode are secondary batteries. In order to prevent wasteful consumption by moving to another electrode through the inside, a separator for electrically insulating the anode and the cathode is included.

図１は本発明の一実施例に係る二次電池用電極の断面図である。   FIG. 1 is a cross-sectional view of an electrode for a secondary battery according to an embodiment of the present invention.

図１に例示された通り、本発明の一実施例に係る二次電池用電極１００は、第１面Ｓ１とその反対側の第２面Ｓ２を有する電解銅箔１１０、前記第１面Ｓ１上の第１活物質層１２０ａ、および前記第２面Ｓ２上の第２活物質層１２０ｂを含む。図１は、前記電解銅箔１１０の第１および第２面Ｓ１、Ｓ２の両面上に活物質層１２０ａ、１２０ｂがそれぞれ形成された例を示しているが、本発明はこれに限定されず、本発明の二次電池用電極１００は活物質層として前記第１および第２活物質層１２０ａ、１２０ｂのうちいずれか一つのみを含むこともできる。   As illustrated in FIG. 1, the secondary battery electrode 100 according to an embodiment of the present invention includes an electrolytic copper foil 110 having a first surface S <b> 1 and a second surface S <b> 2 on the opposite side, on the first surface S <b> 1. The first active material layer 120a and the second active material layer 120b on the second surface S2. FIG. 1 shows an example in which active material layers 120a and 120b are formed on both surfaces of the first and second surfaces S1 and S2 of the electrolytic copper foil 110, respectively, but the present invention is not limited thereto. The secondary battery electrode 100 of the present invention may include only one of the first and second active material layers 120a and 120b as an active material layer.

リチウム二次電池において、陽極活物質と結合する陽極集電体としてはアルミホイル（ｆｏｉｌ）が使われ、陰極活物質と結合する陰極集電体としては電解銅箔が使われるのが一般的である。   In a lithium secondary battery, an aluminum foil is used as an anode current collector combined with an anode active material, and an electrolytic copper foil is used as a cathode current collector combined with a cathode active material. is there.

本発明の一実施例によると、前記二次電池用電極１００はリチウム二次電池の陰極に使われ、前記電解銅箔１１０は陰極集電体として機能し、前記第１および第２活物質層１２０ａ、１２０ｂは陰極活物質を含む。   According to an embodiment of the present invention, the secondary battery electrode 100 is used as a cathode of a lithium secondary battery, the electrolytic copper foil 110 functions as a cathode current collector, and the first and second active material layers are used. 120a and 120b contain a cathode active material.

図１に例示された通り、本発明の電解銅箔１１０は、マット面（ｍａｔｔｅ ｓｕｒｆａｃｅ）ＭＳおよびシャイニー面（ｓｈｉｎｙ ｓｕｒｆａｃｅ）ＳＳを含む銅層１１１、前記銅層１１１の前記マット面ＭＳ上の第１保護層１１２ａ、および前記銅層１１１の前記シャイニー面ＳＳ上の第２保護層１１２ｂを含む。   As illustrated in FIG. 1, the electrolytic copper foil 110 of the present invention includes a copper layer 111 including a matte surface MS and a shiny surface SS, and a copper layer 111 on the mat surface MS of the copper layer 111. A first protective layer 112a, and a second protective layer 112b on the shiny surface SS of the copper layer 111.

前記マット面ＭＳは、前記電解銅箔１１０の第１面Ｓ１に向かう銅層１１１の面であり、前記シャイニー面ＳＳは前記電解銅箔１１０の第２面Ｓ２に向かう銅層１１１の面である。   The mat surface MS is a surface of the copper layer 111 facing the first surface S1 of the electrolytic copper foil 110, and the shiny surface SS is a surface of the copper layer 111 facing the second surface S2 of the electrolytic copper foil 110. .

本発明の銅層１１１は電気メッキを通じて回転電極ドラム上に形成され得るが、前記シャイニー面ＳＳは電気メッキの過程で前記回転電極ドラムと接触した面を指し示し、前記マット面ＭＳは前記シャイニー面ＳＳの反対側の面を指し示す。   The copper layer 111 of the present invention may be formed on the rotating electrode drum through electroplating, but the shiny surface SS indicates a surface in contact with the rotating electrode drum in the process of electroplating, and the mat surface MS is the shiny surface SS. Point to the opposite side.

シャイニー面ＳＳがマット面ＭＳと比べてさらに低い表面粗さＲｚを有するのが一般的であるが、本発明はこれに限定されず、シャイニー面ＳＳの表面粗さＲｚがマット面ＭＳの表面粗さＲｚと同一であるかより高くてもよい。   Generally, the shiny surface SS has a lower surface roughness Rz than the mat surface MS, but the present invention is not limited to this, and the surface roughness Rz of the shiny surface SS is the surface roughness of the mat surface MS. It may be equal to or higher than Rz.

前記第１および第２保護層１１２ａ、１１２ｂは、前記銅層１１１の腐食を防止し、耐熱性を向上させるためのものであって、クロム（Ｃｒ）を含むことができる。   The first and second protective layers 112a and 112b are for preventing corrosion of the copper layer 111 and improving heat resistance, and may include chromium (Cr).

本発明の電解銅箔１１０は常温（２５±１５℃）で２１〜５８ｋｇｆ／ｍｍ２の降伏強度を有することができる。前記降伏強度は万能試験機（ＵＴＭ）を利用して測定するが、この時、サンプルの幅は１２．７ｍｍであり、Ｇｒｉｐ間の距離は５０ｍｍであり、測定速度は５０ｍｍ／ｍｉｎである。 The electrolytic copper foil 110 of the present invention can have a yield strength of 21 to 58 kgf / mm 2 at room temperature (25 ± 15 ° C.). The yield strength is measured using a universal testing machine (UTM). At this time, the width of the sample is 12.7 mm, the distance between the grips is 50 mm, and the measurement speed is 50 mm / min.

電解銅箔１１０の降伏強度が２１ｋｇｆ／ｍｍ２未満であると、電極１００の製造過程および／または二次電池の製造過程で加えられる力によって電解銅箔１１０のシワおよび／または折れが発生する危険がある。反面、電解銅箔１１０の降伏強度が５８ｋｇｆ／ｍｍ２を超過すると、二次電池の製造工程の作業性が低下する。 If the yield strength of the electrolytic copper foil 110 is less than 21 kgf / mm 2 , there is a risk that the electrolytic copper foil 110 may be wrinkled and / or broken due to a force applied in the manufacturing process of the electrode 100 and / or the manufacturing process of the secondary battery. There is. On the other hand, when the yield strength of the electrolytic copper foil 110 exceeds 58 kgf / mm 2 , the workability of the secondary battery manufacturing process deteriorates.

本発明の電解銅箔１１０は常温（２５±１５℃）で３％以上の延伸率を有することができる。電解銅箔１１０の延伸率が３％未満であると、電極１００の製造過程および／または二次電池の製造過程で加えられる力によって電解銅箔１１０が延びずに破れる危険が大きくなる。   The electrolytic copper foil 110 of the present invention can have a stretch ratio of 3% or more at room temperature (25 ± 15 ° C.). If the stretching ratio of the electrolytic copper foil 110 is less than 3%, there is a greater risk that the electrolytic copper foil 110 may be broken without being stretched by the force applied in the manufacturing process of the electrode 100 and / or the manufacturing process of the secondary battery.

本発明の電解銅箔１１０は４〜３０μｍの厚さを有することができる。   The electrolytic copper foil 110 of the present invention can have a thickness of 4 to 30 μm.

前記第１および第２活物質層１２０ａ、１２０ｂは、互いに独立して、炭素；Ｓｉ、Ｇｅ、Ｓｎ、Ｌｉ、Ｚｎ、Ｍｇ、Ｃｄ、Ｃｅ、ＮｉまたはＦｅの金属；前記金属を含む合金；前記金属の酸化物；および前記金属と炭素の複合体からなる群から選択される一つ以上の活物質を陰極活物質として含むことができる。   The first and second active material layers 120a and 120b are, independently of each other, carbon; Si, Ge, Sn, Li, Zn, Mg, Cd, Ce, Ni, or Fe metal; an alloy containing the metal; One or more active materials selected from the group consisting of metal oxides; and metal and carbon composites may be included as the cathode active material.

二次電池の充放電容量を増加させるために、前記第１および第２活物質層１２０ａ、１２０ｂはＳｉを所定量含んだ混合物で形成され得る。   In order to increase the charge / discharge capacity of the secondary battery, the first and second active material layers 120a and 120b may be formed of a mixture containing a predetermined amount of Si.

一方、二次電池の充放電が繰り返されるにつれて、活物質層１２０ａ、１２０ｂのくびれおよび膨張が交互に発生し、これは前記活物質層１２０ａ、１２０ｂと前記電解銅箔１１０の分離を誘発して二次電池の充放電効率を低下させる。したがって、二次電池が一定水準以上の容量維持率および寿命を確保するためには（すなわち、二次電池の充放電効率の低下を抑制するためには）、前記電解銅箔１１０が前記活物質に対して優れたコーティング性を有することによって前記電解銅箔１１０と活物質層１２０ａ、１２０ｂ間の接着強度が高くなければならない。   Meanwhile, as the secondary battery is repeatedly charged and discharged, the active material layers 120a and 120b are alternately constricted and expanded, which induces separation of the active material layers 120a and 120b and the electrolytic copper foil 110. Reduce the charge / discharge efficiency of the secondary battery. Therefore, in order for the secondary battery to ensure a capacity maintenance rate and a life of a certain level or more (that is, to suppress a decrease in charge / discharge efficiency of the secondary battery), the electrolytic copper foil 110 is used as the active material. Therefore, the adhesive strength between the electrolytic copper foil 110 and the active material layers 120a and 120b must be high.

一般に、前記電解銅箔１１０の表面粗さＲｚの制御を通じて電解銅箔１１０と活物質層１２０ａ、１２０ｂ間の接着強度を向上させることができると知られている。前記表面粗さＲｚは、例えばＭａｈｒ社のＭａｈｒｓｕｒｆ Ｍ３００粗さ計を利用してＪＩＳＢ０６０１（２００１）規格に沿って測定され得る［測定長さ：４ｍｍ （ｃｕｔ ｏｆｆ区間は除外）］．   In general, it is known that the adhesive strength between the electrolytic copper foil 110 and the active material layers 120a and 120b can be improved by controlling the surface roughness Rz of the electrolytic copper foil 110. The surface roughness Rz can be measured according to JISB0601 (2001) standard using, for example, a Mahrsurf M300 roughness meter manufactured by Mahr [measurement length: 4 mm (excluding cut off section)].

本発明の一実施例によると、前記電解銅箔１１０の第１および第２面Ｓ１、Ｓ２のそれぞれの表面粗さＲｚは２．５μｍ以下であり得る。前記表面粗さＲｚが２．５μｍを超過する場合には、電解銅箔１１０の第１および第２面Ｓ１、Ｓ２が過度に不均一であるため、陰極活物質のコーティング均一性が低下し、このため、電解銅箔１１０と第１および第２活物質層１２０ａ、１２０ｂの間の密着力が顕著に低下する。   According to an embodiment of the present invention, the surface roughness Rz of each of the first and second surfaces S1 and S2 of the electrolytic copper foil 110 may be 2.5 μm or less. When the surface roughness Rz exceeds 2.5 μm, the first and second surfaces S1, S2 of the electrolytic copper foil 110 are excessively non-uniform, so that the coating uniformity of the cathode active material decreases, For this reason, the adhesive force between the electrolytic copper foil 110 and the first and second active material layers 120a and 120b is significantly reduced.

しかし、実際には、表面粗さＲｚが適切に調整された（例えば、２．５μｍ以下に調整された）電解銅箔１１０が仕様で要求される電解銅箔１１０と活物質層１２０ａ、１２０ｂ間の接着力を必ずしも満足させるとは限らない。すなわち、２．５μｍ以下記の表面粗さＲｚを有する電解銅箔１１０が業界で要求される９０％以上の二次電池の容量維持率（５００回充／放電後）を常に担保できるとは言えない。   However, in practice, the electrolytic copper foil 110 whose surface roughness Rz is appropriately adjusted (for example, adjusted to 2.5 μm or less) is required between the electrolytic copper foil 110 and the active material layers 120a and 120b. It does not always satisfy the adhesive strength of. That is, it can be said that the electrolytic copper foil 110 having a surface roughness Rz of 2.5 μm or less can always guarantee the 90% or more secondary battery capacity maintenance rate (after 500 charge / discharge) required in the industry. Absent.

特に、二次電池の高容量化のために前記活物質層１２０ａ、１２０ｂがＳｉを含む場合、電解銅箔１１０の表面粗さＲｚと二次電池の容量維持率の間の関連性はさらに低いと示された。   In particular, when the active material layers 120a and 120b contain Si in order to increase the capacity of the secondary battery, the relationship between the surface roughness Rz of the electrolytic copper foil 110 and the capacity retention rate of the secondary battery is even lower. It was shown.

本発明によると、９０％以上の二次電池の容量維持率を担保できる程度に十分に大きな電解銅箔１１０と活物質層１２０ａ、１２０ｂ間の接着力を確保するにおいて、電解銅箔１１０のピーク粗さ（ｐｅａｋ ｒｏｕｇｈｎｅｓｓ：Ｒｐ）が表面粗さＲｚよりも重要な因子であることが確認された。   According to the present invention, the peak of the electrolytic copper foil 110 is ensured in ensuring a sufficiently large adhesive force between the electrolytic copper foil 110 and the active material layers 120a and 120b to ensure a capacity retention rate of 90% or more of the secondary battery. It was confirmed that the roughness of the peak (Rp) is more important than the surface roughness Rz.

以下、図２を参照して電解銅箔１１０のピーク粗さ（Ｒｐ）を具体的に説明する。   Hereinafter, the peak roughness (Rp) of the electrolytic copper foil 110 will be specifically described with reference to FIG.

本発明において、「ピーク粗さ（Ｒｐ）」は、ＪＩＳＢ０６０１（２００１）規格に沿って測定され、図２の表面粗さプロファイルに表示した通り、表面粗さプロファイル（サンプリング長さ：４ｍｍ）で最も高いピークの平均線（ｍｅａｎ ｌｉｎｅ）からの高さを意味する。   In the present invention, the “peak roughness (Rp)” is measured according to the JISB0601 (2001) standard, and is the highest in the surface roughness profile (sampling length: 4 mm) as indicated in the surface roughness profile of FIG. It means the height from the mean line of the high peak.

本発明の一実施例によると、前記電解銅箔１１０の第１および第２面Ｓ１、Ｓ２のそれぞれは０．３６〜１．６９μｍのピーク粗さ（Ｒｐ）を有し、前記第１面Ｓ１のピーク粗さ（Ｒｐ）と前記第２面Ｓ２のピーク粗さ（Ｒｐ）の差は０．６μｍ以下である。   According to an embodiment of the present invention, each of the first and second surfaces S1 and S2 of the electrolytic copper foil 110 has a peak roughness (Rp) of 0.36 to 1.69 μm, and the first surface S1. The difference between the peak roughness (Rp) and the peak roughness (Rp) of the second surface S2 is 0.6 μm or less.

前記第１および第２面Ｓ１、Ｓ２のピーク粗さ（Ｒｐ）が０．３６μｍ未満であると、陰極活物質と接触できる電解銅箔１１０の活性非表面積が過度に小さいため、電解銅箔１１０と第１および第２活物質層１２０ａ、１２０ｂの間に十分な密着力を確保することができない。反面、前記第１および第２面Ｓ１、Ｓ２のピーク粗さ（Ｒｐ）が１．６９μｍを超過すると、陰極活物質のコーティング均一性が低下し、このため、電解銅箔１１０と第１および第２活物質層１２０ａ、１２０ｂの間の密着力が顕著に低下する。また、二次電池の充放電時に１．６９μｍを超過するピークに応力が集中して陰極活物質が電解銅箔１１０から分離され、その結果、前記二次電池の容量維持率が低下する。   When the peak roughness (Rp) of the first and second surfaces S1 and S2 is less than 0.36 μm, the active non-surface area of the electrolytic copper foil 110 that can come into contact with the cathode active material is excessively small. And sufficient adhesion cannot be ensured between the first and second active material layers 120a and 120b. On the other hand, when the peak roughness (Rp) of the first and second surfaces S1 and S2 exceeds 1.69 μm, the coating uniformity of the cathode active material is reduced. The adhesion between the two active material layers 120a and 120b is significantly reduced. Also, stress concentrates on the peak exceeding 1.69 μm during charge / discharge of the secondary battery, and the cathode active material is separated from the electrolytic copper foil 110. As a result, the capacity retention rate of the secondary battery is lowered.

また、前記第１面Ｓ１のピーク粗さ（Ｒｐ）と前記第２面Ｓ２のピーク粗さ（Ｒｐ）の差は０．６μｍを超過すると、前記第１面Ｓ１と第１活物質層１２０ａの密着力および前記第２面Ｓ２と第２活物質層１２０ｂの密着力間の差が過度に大きくなるが、これは二次電池の容量維持率の低下をもたらす。   In addition, if the difference between the peak roughness (Rp) of the first surface S1 and the peak roughness (Rp) of the second surface S2 exceeds 0.6 μm, the first surface S1 and the first active material layer 120a The difference between the adhesion force and the adhesion force between the second surface S2 and the second active material layer 120b becomes excessively large, which leads to a decrease in the capacity retention rate of the secondary battery.

本発明によると、電解銅箔１１０と活物質層１２０ａ、１２０ｂ間の接着力を確保するにおいて、電解銅箔１１０の第１および第２面Ｓ１、Ｓ２でのクロム（Ｃｒ）付着量も同様に重要な因子であることが確認された。前記クロム（Ｃｒ）付着量は原子吸収分光器（Ａｔｏｍｉｃ Ａｂｓｏｒｐｔｉｏｎ Ｓｐｅｃｔｒｏｍｅｔｒｙ：ＡＡＳ）の分析を通じて測定され得る。   According to the present invention, in securing the adhesive force between the electrolytic copper foil 110 and the active material layers 120a and 120b, the chromium (Cr) adhesion amount on the first and second surfaces S1 and S2 of the electrolytic copper foil 110 is also the same. It was confirmed to be an important factor. The amount of chromium (Cr) deposited can be measured through analysis of an atomic absorption spectrometer (AAS).

例えば、電解銅箔１１０の第２面Ｓ２をテープでマスキングし、切断することによって１０ｃｍ×１０ｃｍのサンプルを得た後、前記電解銅箔１１０に孔ができないように注意しつつ、前記電解銅箔１１０の第１面Ｓ１を硝酸水溶液（商用硝酸と水を１：１で混合）で溶かす。このように生成された溶液を水で希釈して５０ｍＬの希釈液を得た後、前記希釈液を２５℃で原子吸収分光器（ＡＡＳ）で分析して前記電解銅箔１１０の第１面Ｓ１のクロム付着量を測定することができる。これと類似の方法で前記電解銅箔１１０の第２面Ｓ２のクロム付着量も測定することができる。   For example, after the second surface S2 of the electrolytic copper foil 110 is masked with a tape and cut to obtain a sample of 10 cm × 10 cm, the electrolytic copper foil 110 is carefully taken so as not to have a hole. The first surface S1 of 110 is dissolved with an aqueous nitric acid solution (combined commercial nitric acid and water are mixed 1: 1). The solution thus generated is diluted with water to obtain a 50 mL diluted solution, and then the diluted solution is analyzed with an atomic absorption spectrometer (AAS) at 25 ° C. to form the first surface S1 of the electrolytic copper foil 110. Can be measured. A chromium adhesion amount on the second surface S2 of the electrolytic copper foil 110 can also be measured by a method similar to this.

本発明の一実施例によると、前記第１および第２面のそれぞれにおけるクロム（Ｃｒ）付着量は０．５〜５．５ｍｇ／ｍ２である。クロム（Ｃｒ）付着量が０．５ｍｇ／ｍ２未満であると、酸素が活物質層１２０ａ、１２０ｂを通過して銅層１１１の表面の酸化を誘発し、その結果、電解銅箔１１０と陰極活物質の間の十分な化学的結合を提供することができない。反面、クロム（Ｃｒ）付着量が５．５ｍｇ／ｍ２を超過すると電解銅箔１１０の表面の疏水性（ｈｙｄｒｏｐｈｏｂｉｃｉｔｙ）が増加して陰極活物質に対する化学的親和度低下し、その結果、電解銅箔１１０と陰極活物質の間の十分な化学的結合を提供することができない。 According to an embodiment of the present invention, the chromium (Cr) adhesion amount on each of the first and second surfaces is 0.5 to 5.5 mg / m 2 . If the chromium (Cr) adhesion amount is less than 0.5 mg / m 2 , oxygen passes through the active material layers 120a and 120b and induces oxidation of the surface of the copper layer 111. As a result, the electrolytic copper foil 110 and the cathode It cannot provide a sufficient chemical bond between the active materials. On the other hand, if the chromium (Cr) deposition amount exceeds 5.5 mg / m 2 , the hydrophobity of the surface of the electrolytic copper foil 110 increases and the chemical affinity for the cathode active material decreases, and as a result, the electrolytic copper It is not possible to provide a sufficient chemical bond between the foil 110 and the cathode active material.

また、本発明の一実施例によると、作業性の低下を引き起こし得る電解銅箔１１０のカールを最小化するために、前記第１および第２面Ｓ１、Ｓ２でのクロム（Ｃｒ）付着量差は２．５ｍｇ／ｍ２以下であり得る。 In addition, according to an embodiment of the present invention, in order to minimize curling of the electrolytic copper foil 110 that may cause a decrease in workability, a difference in the amount of chromium (Cr) attached on the first and second surfaces S1 and S2. May be 2.5 mg / m 2 or less.

以下では、本発明の一実施例に係る電解銅箔１１０の製造方法を具体的に説明する。   Below, the manufacturing method of the electrolytic copper foil 110 which concerns on one Example of this invention is demonstrated concretely.

本発明の方法は、銅層１１１を形成する段階および前記銅層１１１上に保護層１１２ａ、１１２ｂを形成する段階を含む。   The method of the present invention includes forming a copper layer 111 and forming protective layers 112 a and 112 b on the copper layer 111.

まず、５０〜１００ｇ／Ｌの銅イオン、５０〜１５０ｇ／Ｌの硫酸、３〜１２ｐｐｍのビス（３−スルホプロピル）ジスルフィド（ＳＰＳ）、および５０ｐｐｍ以下の塩素を含む電解液を準備する。   First, an electrolytic solution containing 50 to 100 g / L of copper ions, 50 to 150 g / L of sulfuric acid, 3 to 12 ppm of bis (3-sulfopropyl) disulfide (SPS), and 50 ppm or less of chlorine is prepared.

引き続き、４０〜６０℃の前記電解液内に互いに離隔して配置された電極板および回転電極ドラムを４０〜８０Ａ／ｄｍ２の電流密度で通電させて電気メッキを行うことによって前記銅層１１１を前記回転電極ドラム上に形成させる。 Subsequently, the copper layer 111 is formed by performing electroplating by energizing an electrode plate and a rotating electrode drum that are spaced apart from each other in the electrolyte at 40 to 60 ° C. at a current density of 40 to 80 A / dm 2. It is formed on the rotating electrode drum.

本発明によると、前記電気メッキが行われる間、前記電解液内の全炭素量（Ｔｏｔａｌ Ｃａｒｂｏｎ：ＴＣ）が０．２５ｇ／Ｌ以下に維持されるように前記電解液が管理される。全炭素量（ＴＣ）は全有機炭素（Ｔｏｔａｌ Ｏｒｇａｎｉｃ Ｃａｒｂｏｎ：ＴＯＣ）および全無機炭素（Ｔｏｔａｌ Ｉｎｏｒｇａｎｉｃ Ｃａｒｂｏｎ：ＴＩＣ）から構成され、ＴＣ測定設備を通じて分析され得る。   According to the present invention, during the electroplating, the electrolytic solution is managed so that the total carbon amount (Total Carbon: TC) in the electrolytic solution is maintained at 0.25 g / L or less. Total carbon (TC) is composed of total organic carbon (TOC) and total inorganic carbon (TOC), and can be analyzed through a TC measurement facility.

電解液の全炭素量（ＴＣ）を０．２５ｇ／Ｌ以下に維持させるために、高純度の銅ワイヤーを６００〜９００℃で３０〜６０分の間熱処理して有機物を焼き、前記熱処理された銅ワイヤーを酸洗し、前記酸洗した銅ワイヤーを硫酸に投入することによって不純物が全くまたは殆どない電解液を準備する。   In order to maintain the total carbon content (TC) of the electrolytic solution at 0.25 g / L or less, a high-purity copper wire was heat-treated at 600 to 900 ° C. for 30 to 60 minutes to bake organic matter, and the heat treatment was performed. The copper wire is pickled, and the pickled copper wire is put into sulfuric acid to prepare an electrolyte solution having no or little impurities.

電解液の全炭素量（ＴＣ）を０．２５ｇ／Ｌ以下に維持させるために、オゾン処理を通じて電解液内の有機物を分解することによって前記全炭素量（ＴＣ）を低くすることもできる。また、前記電気メッキが行われる間過酸化水素および空気を前記電解液に投入することによって前記電解液の清浄度を向上させることができる。   In order to maintain the total carbon amount (TC) of the electrolytic solution at 0.25 g / L or less, the total carbon amount (TC) can be lowered by decomposing organic substances in the electrolytic solution through ozone treatment. Also, the cleanliness of the electrolyte can be improved by introducing hydrogen peroxide and air into the electrolyte during the electroplating.

本発明によると、前記電気メッキが行われる間、前記電解液内のスカンジウム（Ｓｃ）とイットリウム（Ｙ）の総濃度は、３５０ｍｇ／Ｌ以下に維持される。また、電解液内でスカンジウム（Ｓｃ）とイットリウム（Ｙ）は、それぞれ０．１ｍｇ／Ｌ以上の濃度を有することができる。例えば、電解液内でスカンジウム（Ｓｃ）とイットリウム（Ｙ）は、それぞれ０．１〜０．２ｍｇ／Ｌの濃度を有することができる。   According to the present invention, the total concentration of scandium (Sc) and yttrium (Y) in the electrolyte is maintained at 350 mg / L or less during the electroplating. In the electrolyte, scandium (Sc) and yttrium (Y) can each have a concentration of 0.1 mg / L or more. For example, scandium (Sc) and yttrium (Y) can each have a concentration of 0.1 to 0.2 mg / L in the electrolyte.

前記回転電極ドラムの表面（電気メッキによって銅が析出される面）の研磨の程度も電解銅箔１１０の第２面Ｓ２の表面粗さＲｚ、ピーク粗さ（Ｒｐ）、およびクロム付着量を制御する一つの要素である。本発明によると、＃８００〜＃１５００の粒度（Ｇｒｉｔ）を有する研磨ブラシで前記回転電極ドラムの表面が研磨される。   The degree of polishing of the surface of the rotating electrode drum (surface on which copper is deposited by electroplating) also controls the surface roughness Rz, peak roughness (Rp), and chromium adhesion amount of the second surface S2 of the electrolytic copper foil 110. Is one element to do. According to the present invention, the surface of the rotary electrode drum is polished with a polishing brush having a particle size (Grit) of # 800 to # 1500.

＃８００〜＃１５００の粒度（Ｇｒｉｔ）を有する研磨ブラシで前記回転電極ドラムの表面を研磨し、電解液の全炭素量（ＴＣ）、およびスカンジウム（Ｓｃ）とイットリウム（Ｙ）の総濃度を０．２５ｇ／Ｌ以下および３５０ｍｇ／Ｌ以下にそれぞれ管理し、４０〜８０Ａ／ｄｍ２の電流密度を適用することによって、電解銅箔１１０の第１および第２面Ｓ１、Ｓ２のピーク粗さ（Ｒｐ）およびピーク粗さ（Ｒｐ）の差を本発明の範囲［ピーク粗さ（Ｒｐ）：０．３６〜１．６９μｍ；ピーク粗さ（Ｒｐ）の差：０．６μｍ以下］内にそれぞれ制御することができる。 The surface of the rotary electrode drum is polished with a polishing brush having a particle size (Grit) of # 800 to # 1500, and the total carbon content (TC) of the electrolyte and the total concentration of scandium (Sc) and yttrium (Y) are reduced to 0. The peak roughness (Rp) of the first and second surfaces S1 and S2 of the electrolytic copper foil 110 is controlled by applying a current density of 40 to 80 A / dm 2 , respectively managed at .25 g / L or less and 350 mg / L or less. ) And peak roughness (Rp) are controlled within the range of the present invention [peak roughness (Rp): 0.36 to 1.69 μm; difference in peak roughness (Rp): 0.6 μm or less], respectively. be able to.

前記電気メッキが行われる間前記電解液から固形不純物を除去するための連続（または循環）濾過を３１〜４５ｍ３／ｈｒの流量で行うことができる。前記流量が３１ｍ３／ｈｒ未満であると、流速が低くなって過電圧が増加し、銅層１１１が不均一に形成される。反面、前記流量が４５ｍ３／ｈｒを超過すると、フィルタの損傷が誘発されて電解液内に異物が流入して電解液の全炭素量（ＴＣ）が増加する。 During the electroplating, continuous (or circulating) filtration for removing solid impurities from the electrolytic solution can be performed at a flow rate of 31 to 45 m 3 / hr. When the flow rate is less than 31 m 3 / hr, the flow rate is lowered, the overvoltage is increased, and the copper layer 111 is formed unevenly. On the other hand, when the flow rate exceeds 45 m 3 / hr, damage to the filter is induced, foreign matter flows into the electrolytic solution, and the total carbon amount (TC) of the electrolytic solution increases.

選択的事項として、前記電解液はヒドロキシエチルセルロース（ＨＥＣ）、有機硫化物、有機窒化物、グリコール系高分子、およびチオ尿素（ｔｈｉｏｕｒｅａ）系化合物から構成されたグループから選択される少なくとも一つの有機添加剤をさらに含むことができる。   As an option, the electrolyte solution includes at least one organic additive selected from the group consisting of hydroxyethyl cellulose (HEC), organic sulfides, organic nitrides, glycol-based polymers, and thiourea-based compounds. An agent can further be included.

前記のように製造された銅層１１１を０．５〜１．５ｇ／ＬのＣｒを含む防錆液内に浸漬（例えば、常温に２〜２０秒の間）させた後乾燥させることによって前記銅層１１１上に第１および第２保護層１１２ａ、１１２ｂをそれぞれ形成させる。   The copper layer 111 manufactured as described above is immersed in a rust preventive solution containing 0.5 to 1.5 g / L of Cr (for example, at room temperature for 2 to 20 seconds) and then dried. First and second protective layers 112a and 112b are formed on the copper layer 111, respectively.

前記防錆液は、シラン化合物と窒素化合物のうち少なくとも１種以上をさらに含むことができる。例えば、前記防錆液は、０．５〜１．５ｇ／ＬのＣｒおよび０．５〜１．５ｇ／Ｌのシラン化合物を含むことができる。   The rust preventive liquid may further include at least one of a silane compound and a nitrogen compound. For example, the rust preventive liquid may contain 0.5 to 1.5 g / L Cr and 0.5 to 1.5 g / L silane compound.

このように製造された本発明の電解銅箔１１０上に陰極活物質をコーティングすることによって本発明の二次電池用電極（すなわち、陰極）が製造され得る。   The secondary battery electrode (that is, the cathode) of the present invention can be manufactured by coating the cathode active material on the electrolytic copper foil 110 of the present invention thus manufactured.

前記陰極活物質は、炭素；Ｓｉ、Ｇｅ、Ｓｎ、Ｌｉ、Ｚｎ、Ｍｇ、Ｃｄ、Ｃｅ、ＮｉまたはＦｅの金属；前記金属を含む合金；前記金属の酸化物；および前記金属と炭素の複合体からなる群から選択され得る。   The cathode active material is carbon; a metal of Si, Ge, Sn, Li, Zn, Mg, Cd, Ce, Ni, or Fe; an alloy containing the metal; an oxide of the metal; and a composite of the metal and carbon Can be selected from the group consisting of

例えば、１００重量部の陰極活物質用炭素に１〜３重量部のスチレンブタジエンゴム（ＳＢＲ）および１〜３重量部のカルボキシメチルセルロース（ＣＭＣ）を混合した後、蒸溜水を溶剤に使ってスラリーを調製する。引き続き、ドクターブレードを利用して前記電解銅箔１１０上に２０〜１００μｍ厚さに前記スラリーを塗布し、１１０〜１３０℃で０．５〜１．５ｔｏｎ／ｃｍ２の圧力でプレスする。 For example, 1 to 3 parts by weight of styrene butadiene rubber (SBR) and 1 to 3 parts by weight of carboxymethylcellulose (CMC) are mixed with 100 parts by weight of carbon for cathode active material, and then slurry is prepared using distilled water as a solvent. Prepare. Subsequently, the slurry is applied to the electrolytic copper foil 110 to a thickness of 20 to 100 μm using a doctor blade, and pressed at 110 to 130 ° C. and a pressure of 0.5 to 1.5 ton / cm 2 .

以上の方法で製造された本発明の二次電池用電極（陰極）と共に通常の陽極、電解質、および分離膜を利用してリチウム二次電池を製造することができる。   A lithium secondary battery can be manufactured using a normal anode, an electrolyte, and a separation membrane together with the secondary battery electrode (cathode) of the present invention manufactured by the above method.

以下では、実施例および比較例を通じて本発明を具体的に説明する。ただし、下記の実施例は本発明の理解を助けるためのものに過ぎず、本発明の権利範囲はこれらの実施例に制限されない。   Hereinafter, the present invention will be described in detail through examples and comparative examples. However, the following examples are only for helping understanding of the present invention, and the scope of rights of the present invention is not limited to these examples.

実施例１〜３および比較例１〜５
電解液内に互いに離隔して配置された電極板および回転電極ドラムを５０Ａ／ｄｍ２の電流密度で通電させることによって銅層を形成した。前記電解液は、７５ｇ／Ｌの銅イオン、１００ｇ／Ｌの硫酸、８ｐｐｍのビス（３−スルホプロピル）ジスルフィド（ＳＰＳ）、および２０ｐｐｍの塩素を含んでおり、５５℃に維持された。電気メッキが行われる間、前記電解液から固形不純物を除去するための連続濾過が３７ｍ３／ｈｒの流量で行われた。前記電解液内のエチレンチオ尿素（ｅｔｈｙｌｅｎｅ ｔｈｉｏｕｒｅａ：ＥＴＵ）の含量、前記電解液内の全炭素量（ＴＣ）、前記電解液内のスカンジウム（Ｓｃ）とイットリウム（Ｙ）の総濃度、および前記回転電極ドラムの表面の研磨に使われた研磨ブラシの粒度は下記の表１のとおりである。前記電気メッキを通じて形成された銅層を防錆液に浸漬させた後、乾燥させることによって電解銅箔を完成した。 Examples 1-3 and Comparative Examples 1-5
A copper layer was formed by energizing an electrode plate and a rotating electrode drum that were spaced apart from each other in the electrolytic solution at a current density of 50 A / dm 2 . The electrolyte contained 75 g / L copper ions, 100 g / L sulfuric acid, 8 ppm bis (3-sulfopropyl) disulfide (SPS), and 20 ppm chlorine, and was maintained at 55 ° C. During electroplating, continuous filtration to remove solid impurities from the electrolyte was performed at a flow rate of 37 m 3 / hr. The content of ethylene thiourea (ETU) in the electrolyte, the total carbon content (TC) in the electrolyte, the total concentration of scandium (Sc) and yttrium (Y) in the electrolyte, and the rotating electrode The particle size of the polishing brush used for polishing the surface of the drum is as shown in Table 1 below. The copper layer formed through the electroplating was immersed in an antirust solution and then dried to complete an electrolytic copper foil.

前記のように製造された実施例１−３および比較例１−５の電解銅箔の第１面（銅層のマット面が向いている電解銅箔の面）およびその反対側の第２面のピーク粗さ（Ｒｐ）、そして前記電解銅箔の降伏強度を下記のようにそれぞれ求めた。また、実施例１−３および比較例１−５の電解銅箔で製造された陰極を含む二次電池の容量維持率を下記のようにそれぞれ求めた。前記測定結果を下記の表２に表わした。   The first surface of the electrolytic copper foil of Examples 1-3 and Comparative Example 1-5 manufactured as described above (the surface of the electrolytic copper foil facing the mat surface of the copper layer) and the second surface on the opposite side The peak roughness (Rp) and the yield strength of the electrolytic copper foil were determined as follows. Moreover, the capacity retention rate of the secondary battery containing the cathode manufactured with the electrolytic copper foil of Example 1-3 and Comparative Example 1-5 was calculated | required as follows, respectively. The measurement results are shown in Table 2 below.

＊ ピーク粗さ（Ｒｐ）（μｍ）
電解銅箔の第１および第２面ごとに任意の３地点のピーク粗さ（Ｒｐ）を測定してこれらの平均値を求めた。 * Peak roughness (Rp) (μm)
The peak roughness (Rp) at three arbitrary points was measured for each of the first and second surfaces of the electrolytic copper foil, and the average value thereof was determined.

ＪＩＳＢ０６０１（２００１）規格に沿って、表面粗さプロファイルで最も高いピーク（ｈｉｇｈｅｓｔ ｐｅａｋ）の平均線（ｍｅａｎ ｌｉｎｅ）からの高さ（ｈｅｉｇｈｔ）を測定することによって、各地点のピーク粗さ（Ｒｐ）を求めた。この時、使われた粗さ計はＭｉｔｓｕｔｏｙｏ社のＳＪ−３１０粗さ計であり、スキャン速度は０．１ｍｍ／ｓｅｃであり、１回の測定長さは４ｍｍであり、プローブサイズは５μｍであった。   In accordance with JISB0601 (2001) standard, the peak roughness (Rp) of each point is measured by measuring the height from the mean line of the highest peak in the surface roughness profile. Asked. At this time, the roughness meter used was an SJ-310 roughness meter manufactured by Mitsutoyo, the scan speed was 0.1 mm / sec, the measurement length for one measurement was 4 mm, and the probe size was 5 μm. It was.

＊ 常温（２５±１５℃）での降伏強度（ｋｇｆ／ｍｍ２）
電解銅箔の常温降伏強度は万能試験機（ＵＴＭ）を利用して測定したが、この時、サンプルの幅は１２．７ｍｍであり、Ｇｒｉｐ間の距離は５０ｍｍであり、測定速度は５０ｍｍ／ｍｉｎであった。 * Yield strength at normal temperature (25 ± 15 ° C) (kgf / mm 2 )
The room temperature yield strength of the electrolytic copper foil was measured using a universal testing machine (UTM). At this time, the width of the sample was 12.7 mm, the distance between the grips was 50 mm, and the measurement speed was 50 mm / min. Met.

＊ 二次電池の容量維持率（％）
まず、実施例１−３および比較例１−５の電解銅箔で陰極を製造した。具体的には、陰極活物質用として市販されているカーボン１００重量部にＳＢＲ（スチレンブタジエンゴム）２重量部およびＣＭＣ（カルボキシメチルセルロース）２重量部を混合した。引き続き、この混合物に溶剤である蒸溜水を添加することによってスラリーを製造した。ドクターブレードを利用して前記スラリーを約６０μｍ厚さに電解銅箔（幅：１０ｃｍ）の表面上に塗布し、１２０℃で乾燥させた後、ロールプレス工程（圧力：１ｔｏｎ／ｃｍ２）を行うことによって陰極を製造した。 * Secondary battery capacity maintenance rate (%)
First, the cathode was manufactured with the electrolytic copper foil of Example 1-3 and Comparative Example 1-5. Specifically, 2 parts by weight of SBR (styrene butadiene rubber) and 2 parts by weight of CMC (carboxymethylcellulose) were mixed with 100 parts by weight of carbon commercially available for a cathode active material. Subsequently, a slurry was prepared by adding distilled water as a solvent to the mixture. The slurry is applied to a surface of an electrolytic copper foil (width: 10 cm) to a thickness of about 60 μm using a doctor blade, dried at 120 ° C., and then subjected to a roll press step (pressure: 1 ton / cm 2 ). Thus, a cathode was manufactured.

リチウムマンガン酸化物（Ｌｉ１．１Ｍｎ１．８５Ａｌ０．０５Ｏ４）とｏｒｔｈｏｒｈｏｍｂｉｃ結晶構造のリチウムマンガン酸化物（ｏ−ＬｉＭｎＯ２）を９０：１０の重量比で混合して陽極活物質を製造した。前記陽極活物質、カーボンブラック、およびポリビニリデンフルオライド（ＰＶＤＦ）を８５：１０：５の重量比で有機溶媒であるＮＭＰと混合してスラリーを製造した。前記スラリーを厚さ２０μｍのアルミホイルの両面に塗布した後、乾燥させることによって陽極を製造した。 Lithium manganese oxide (Li 1.1 Mn 1.85 Al 0.05 O 4 ) and orthohombic crystal structure lithium manganese oxide (o-LiMnO 2 ) are mixed at a weight ratio of 90:10 to obtain an anode active material. Manufactured. The anode active material, carbon black, and polyvinylidene fluoride (PVDF) were mixed with NMP, which is an organic solvent, at a weight ratio of 85: 10: 5 to prepare a slurry. The slurry was applied to both sides of an aluminum foil having a thickness of 20 μm, and then dried to produce an anode.

また、エチレンカーボネート（ＥＣ）およびエチルメチルカーボネート（ＥＭＣ）を１：２の重量比で混合した非水性有機溶媒に溶質としてＬｉＰＦ６を１Ｍ溶解させたものを基本電解液とし、この基本電解液９９．５重量％と琥珀酸無水物（ｓｕｃｃｉｎｉｃ ａｎｈｙｄｒｉｄｅ）０．５重量％を混合して二次電池用電解液を製造した。 In addition, a basic electrolyte is obtained by dissolving 1M LiPF 6 as a solute in a non-aqueous organic solvent in which ethylene carbonate (EC) and ethyl methyl carbonate (EMC) are mixed at a weight ratio of 1: 2. An electrolyte solution for a secondary battery was prepared by mixing 0.5% by weight and 0.5% by weight of succinic anhydride.

このように製造された陰極、陽極、および電解液で二次電池を製造した。
引き続き、このように製造された二次電池に対し、４．３Ｖの充電作動電圧および３．４Ｖの放電作動電圧で陽極のｇ当たりの容量を測定し、５０℃で０．２Ｃの充／放電速度で５００回の充／放電実験を行い、二次電池の容量維持率を下記の式１により算出した。業界で要求される二次電池の容量維持率は９０％以上である。 A secondary battery was manufactured using the thus manufactured cathode, anode, and electrolytic solution.
Subsequently, the capacity per g of the anode was measured at a charging operating voltage of 4.3 V and a discharging operating voltage of 3.4 V for the secondary battery manufactured in this manner, and 0.2 C charging / discharging at 50 ° C. The charge / discharge experiment was performed 500 times at a speed, and the capacity retention rate of the secondary battery was calculated by the following formula 1. The capacity maintenance rate of the secondary battery required in the industry is 90% or more.

［式１］
容量維持率（％）＝（５００回目の放電容量／１回目の放電容量）×１００ [Formula 1]
Capacity retention rate (%) = (500th discharge capacity / first discharge capacity) × 100

各電解銅箔ごとに５個のサンプルを取り、前記５個のサンプルで５個の二次電池を前述した方法でそれぞれ製造し、前記５個の二次電池の容量維持率を前述した方法でそれぞれ測定し、この測定値を算術平均することによって前記電解銅箔に該当する「二次電池の容量維持率」を求めた。   Five samples are taken for each electrolytic copper foil, and five secondary batteries are manufactured using the five samples by the above-described method, respectively, and the capacity retention rate of the five secondary batteries is determined by the method described above. Each was measured, and the measured value was arithmetically averaged to determine the “secondary battery capacity maintenance ratio” corresponding to the electrolytic copper foil.

前記の表２から、電解銅箔の第１および第２面のうちいずれか一面でも０．３６μｍ未満のピーク粗さ（Ｒｐ）を有する場合（比較例１および３）、電解銅箔の第１および第２面のうちいずれか一面でも１．６９μｍを超過するピーク粗さ（Ｒｐ）を有する場合（比較例２および４）、そして電解銅箔の第１および第２面のピーク粗さ（Ｒｐ）の差が０．６μｍを超過する場合（比較例５）、二次電池の容量維持率が業界で要求される値（９０％）より顕著に低いことがわかる。   From Table 2 above, when any one of the first and second surfaces of the electrolytic copper foil has a peak roughness (Rp) of less than 0.36 μm (Comparative Examples 1 and 3), the first of the electrolytic copper foil And any one of the second surfaces has a peak roughness (Rp) exceeding 1.69 μm (Comparative Examples 2 and 4), and the peak roughness (Rp) of the first and second surfaces of the electrolytic copper foil ) Exceeds 0.6 μm (Comparative Example 5), it can be seen that the capacity retention rate of the secondary battery is significantly lower than the value required in the industry (90%).

図３および図４は実施例１および比較例１の電解銅箔を利用して製造された二次電池に対して充／放電実験を行った後の陰極の状態をそれぞれ示す写真である。   3 and 4 are photographs showing the state of the cathode after conducting charge / discharge experiments on secondary batteries manufactured using the electrolytic copper foils of Example 1 and Comparative Example 1, respectively.

図３に示した通り、実施例１の電解銅箔で製造された陰極は前記５００回充／放電実験後にも銅層と活物質層が堅固に接着されている。これに反し、図４に示した通り、比較例１の電解銅箔で製造された陰極は前記５００回充／放電実験後に活物質層の相当部分が銅層から分離されていることを確認することができる。   As shown in FIG. 3, in the cathode manufactured by the electrolytic copper foil of Example 1, the copper layer and the active material layer are firmly bonded even after the 500 charge / discharge experiments. On the other hand, as shown in FIG. 4, the cathode manufactured with the electrolytic copper foil of Comparative Example 1 confirms that a substantial part of the active material layer is separated from the copper layer after the 500 charge / discharge experiments. be able to.

１００：二次電池用電極
１１０：電解銅箔
１１１：銅層
１１２ａ：第１保護層
１１２ｂ：第２保護層
１２０ａ：第１活物質層
１２０ｂ：第２活物質層 DESCRIPTION OF SYMBOLS 100: Electrode for secondary batteries 110: Electrolytic copper foil 111: Copper layer 112a: 1st protective layer 112b: 2nd protective layer 120a: 1st active material layer 120b: 2nd active material layer

Claims (16)

第１面とその反対側の第２面を有する電解銅箔において、
前記第１面に向かうマット面（ｍａｔｔｅ ｓｕｒｆａｃｅ）および前記第２面に向かうシャイニー面（ｓｈｉｎｙ ｓｕｒｆａｃｅ）を含む銅層；
前記マット面上の第１保護層；および
前記シャイニー面上の第２保護層を含み、
前記第１および第２面のそれぞれは０．３６〜１．６９μｍのピーク粗さ（ｐｅａｋ ｒｏｕｇｈｎｅｓｓ：Ｒｐ）を有し、
前記第１面のピーク粗さと前記第２面のピーク粗さの差は０．６μｍ以下であることを特徴とする、電解銅箔。 In the electrolytic copper foil having the first surface and the second surface on the opposite side,
A copper layer including a matte surface facing the first surface and a shiny surface facing the second surface;
A first protective layer on the mat surface; and a second protective layer on the shiny surface;
Each of the first and second surfaces has a peak roughness (Rp) of 0.36 to 1.69 μm,
The electrolytic copper foil is characterized in that the difference between the peak roughness of the first surface and the peak roughness of the second surface is 0.6 μm or less. 前記第１および第２保護層のそれぞれはクロム（Ｃｒ）を含み、
前記第１および第２面のそれぞれにおけるクロム（Ｃｒ）付着量は０．５〜５．５ｍｇ／ｍ２であることを特徴とする、請求項１に記載の電解銅箔。 Each of the first and second protective layers includes chromium (Cr);
2. The electrolytic copper foil according to claim 1, wherein a chromium (Cr) adhesion amount on each of the first and second surfaces is 0.5 to 5.5 mg / m 2 . 前記第１面でのクロム（Ｃｒ）付着量と前記第２面でのクロム（Ｃｒ）付着量の差は２．５ｍｇ／ｍ２以下であることを特徴とする、請求項２に記載の電解銅箔。 The electrolysis according to claim 2, wherein the difference between the amount of chromium (Cr) deposited on the first surface and the amount of chromium (Cr) deposited on the second surface is 2.5 mg / m 2 or less. Copper foil. 前記第１および第２面のそれぞれの表面粗さＲｚは２．５μｍ以下であることを特徴とする、請求項１に記載の電解銅箔。   2. The electrolytic copper foil according to claim 1, wherein the surface roughness Rz of each of the first and second surfaces is 2.5 μm or less. ２５±１５℃の常温で２１〜５８ｋｇｆ／ｍｍ２の降伏強度を有することを特徴とする、請求項１に記載の電解銅箔。 2. The electrolytic copper foil according to claim 1, having a yield strength of 21 to 58 kgf / mm 2 at a room temperature of 25 ± 15 ° C. 3. ４〜３０μｍの厚さを有することを特徴とする、請求項１に記載の電解銅箔。   The electrolytic copper foil according to claim 1, wherein the electrolytic copper foil has a thickness of 4 to 30 μm. 第１面とその反対側の第２面を有する電解銅箔；および
前記第１面上の第１活物質層を含み、
前記電解銅箔は、
前記第１面に向かうマット面および前記第２面に向かうシャイニー面を含む銅層；
前記マット面上の第１保護層；および
前記シャイニー面上の第２保護層を含み、
前記第１および第２面のそれぞれは０．３６〜１．６９μｍのピーク粗さ（ｐｅａｋ ｒｏｕｇｈｎｅｓｓ：Ｒｐ）を有し、
前記第１面のピーク粗さと前記第２面のピーク粗さの差は０．６μｍ以下であることを特徴とする、二次電池用電極。 An electrolytic copper foil having a first surface and a second surface opposite thereto; and a first active material layer on the first surface;
The electrolytic copper foil is
A copper layer including a matte surface facing the first surface and a shiny surface facing the second surface;
A first protective layer on the mat surface; and a second protective layer on the shiny surface;
Each of the first and second surfaces has a peak roughness (Rp) of 0.36 to 1.69 μm,
The secondary battery electrode, wherein a difference between the peak roughness of the first surface and the peak roughness of the second surface is 0.6 μm or less. 前記第１および第２保護層のそれぞれはクロム（Ｃｒ）を含み、
前記第１および第２面のそれぞれにおけるクロム（Ｃｒ）付着量は０．５〜５．５ｍｇ／ｍ２であり、
前記第１面でのクロム（Ｃｒ）付着量と前記第２面でのクロム（Ｃｒ）付着量の差は２．５ｍｇ／ｍ２以下であることを特徴とする、請求項７に記載の二次電池用電極。 Each of the first and second protective layers includes chromium (Cr);
The chromium (Cr) adhesion amount on each of the first and second surfaces is 0.5 to 5.5 mg / m 2 ,
The difference between the chromium (Cr) deposition amount on the first surface and the chromium (Cr) deposition amount on the second surface is 2.5 mg / m 2 or less. Secondary battery electrode. 前記電解銅箔は２５±１５℃の常温で２１〜５８ｋｇｆ／ｍｍ２の降伏強度を有することを特徴とする、請求項７に記載の二次電池用電極。 The electrode for a secondary battery according to claim 7, wherein the electrolytic copper foil has a yield strength of 21 to 58 kgf / mm 2 at a room temperature of 25 ± 15 ° C. 前記第２面上の第２活物質層をさらに含み、
前記第１および第２活物質層は、互いに独立して、炭素；Ｓｉ、Ｇｅ、Ｓｎ、Ｌｉ、Ｚｎ、Ｍｇ、Ｃｄ、Ｃｅ、ＮｉまたはＦｅの金属；前記金属を含む合金；前記金属の酸化物；および前記金属と炭素の複合体からなる群から選択される一つ以上の活物質をそれぞれ含む、請求項７に記載の二次電池用電極。 A second active material layer on the second surface;
The first and second active material layers are, independently of each other, carbon; a metal of Si, Ge, Sn, Li, Zn, Mg, Cd, Ce, Ni, or Fe; an alloy containing the metal; an oxidation of the metal And an active material selected from the group consisting of a composite of the metal and carbon. 陽極（ｃａｔｈｏｄｅ）；
請求項７〜請求項１０のいずれか一項に記載された二次電池用電極で構成された陰極（ａｎｏｄｅ）；
前記陽極と陰極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）；および
前記陽極と前記陰極を電気的に絶縁させる分離膜（ｓｅｐａｒａｔｏｒ）を含むことを特徴とする、二次電池。 An anode;
A cathode made of the electrode for a secondary battery according to any one of claims 7 to 10;
A secondary battery comprising: an electrolyte that provides an environment in which lithium ions can move between the anode and the cathode; and a separator that electrically insulates the anode and the cathode. 銅層を形成する段階；および
前記銅層上に保護層を形成する段階を含み、
前記銅層形成段階は、
５０〜１００ｇ／Ｌの銅イオン、５０〜１５０ｇ／Ｌの硫酸、３〜１２ｐｐｍのビス（３−スルホプロピル）ジスルフィド（ＳＰＳ）、および５０ｐｐｍ以下の塩素を含む電解液を準備する段階；および
前記電解液内に互いに離隔して配置された電極板および回転電極ドラムを４０〜８０Ａ／ｄｍ２の電流密度で通電させることによって電気メッキを行う段階を含み、
前記電気メッキが行われる間、前記電解液内の全炭素量（Ｔｏｔａｌ Ｃａｒｂｏｎ：ＴＣ）は０．２５ｇ／Ｌ以下に維持され、前記電解液内のスカンジウム（Ｓｃ）およびイットリウム（Ｙ）の総濃度は３５０ｍｇ／Ｌ以下に維持され、
前記回転電極ドラムの表面は＃８００〜＃１５００の粒度（Ｇｒｉｔ）を有する研磨ブラシで研磨されたことを特徴とする、電解銅箔の製造方法。 Forming a copper layer; and forming a protective layer on the copper layer,
The copper layer forming step includes:
Providing an electrolyte comprising 50-100 g / L copper ions, 50-150 g / L sulfuric acid, 3-12 ppm bis (3-sulfopropyl) disulfide (SPS), and 50 ppm or less chlorine; and the electrolysis Electroplating by energizing an electrode plate and a rotating electrode drum that are spaced apart from each other in the liquid at a current density of 40 to 80 A / dm 2 ;
During the electroplating, the total carbon amount (Total Carbon: TC) in the electrolytic solution is maintained at 0.25 g / L or less, and the total concentration of scandium (Sc) and yttrium (Y) in the electrolytic solution. Is maintained below 350 mg / L,
The method for producing an electrolytic copper foil, wherein the surface of the rotating electrode drum is polished with a polishing brush having a grain size (Grit) of # 800 to # 1500. 前記電解液準備段階は、
銅ワイヤーを６００〜９００℃で３０〜６０分の間熱処理する段階；
前記熱処理された銅ワイヤーを酸洗する段階；および
前記酸洗した銅ワイヤーを硫酸に投入する段階を含むことを特徴とする、請求項１２に記載の電解銅箔の製造方法。 The electrolyte preparation step includes
Heat treating the copper wire at 600-900 ° C. for 30-60 minutes;
The method for producing an electrolytic copper foil according to claim 12, comprising: pickling the heat-treated copper wire; and throwing the pickled copper wire into sulfuric acid. 前記銅層形成段階は、
前記電気メッキが行われる間過酸化水素および空気を前記電解液に投入する段階をさらに含むことを特徴とする、請求項１２に記載の電解銅箔の製造方法。 The copper layer forming step includes:
The method of manufacturing an electrolytic copper foil according to claim 12, further comprising a step of introducing hydrogen peroxide and air into the electrolytic solution during the electroplating. 前記電解液はヒドロキシエチルセルロース（ＨＥＣ）、有機硫化物、有機窒化物、グリコール（ｇｌｙｃｏｌ）系高分子、およびチオ尿素（ｔｈｉｏｕｒｅａ）系化合物から構成されたグループから選択される少なくとも一つの有機添加剤をさらに含むことを特徴とする、請求項１２に記載の電解銅箔の製造方法。   The electrolyte includes at least one organic additive selected from the group consisting of hydroxyethyl cellulose (HEC), organic sulfides, organic nitrides, glycol polymers, and thiourea compounds. The method for producing an electrolytic copper foil according to claim 12, further comprising: 前記保護層形成段階は０．５〜１．５ｇ／ＬのＣｒを含む防錆液内に前記銅層を浸漬させる段階を含むことを特徴とする、請求項１２に記載の電解銅箔の製造方法。   [13] The manufacturing of an electrolytic copper foil according to claim 12, wherein the protective layer forming step includes a step of immersing the copper layer in a rust preventive solution containing 0.5 to 1.5 g / L of Cr. Method.
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