TW201825716A - Electrolytic copper foil having optimized peak roughness, electrode including the same, secondary battery including the same, and method of manufacturing the same - Google Patents

Electrolytic copper foil having optimized peak roughness, electrode including the same, secondary battery including the same, and method of manufacturing the same Download PDF

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TW201825716A
TW201825716A TW107100167A TW107100167A TW201825716A TW 201825716 A TW201825716 A TW 201825716A TW 107100167 A TW107100167 A TW 107100167A TW 107100167 A TW107100167 A TW 107100167A TW 201825716 A TW201825716 A TW 201825716A
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copper foil
electrolytic copper
secondary battery
active material
layer
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TWI682075B (en
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金星玟
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南韓商Ｌｓ美創有限公司
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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

Provided are an electrolytic copper foil having an optimized peak roughness to improve a capacity retention rate of a secondary battery, an electrode including the same, a secondary battery including the same, and a method of manufacturing the same. The electrolytic copper foil includes a first surface and a second surface opposite the first surface, wherein each of the first and second surfaces has a peak roughness (Rp) of 0.36 to 1.69 [mu]m, and a difference between the peak roughness (Rp) of the first surface and the peak roughness (Rp) of the second surface is 0.6 [mu]m or less.

Description

具有優化峰粗糙度的電解銅箔、包含其的電極、包含其的二次電池、及其製造方法Electrolytic copper foil with optimized peak roughness, electrode including the same, secondary battery including the same, and manufacturing method thereof

本發明關於一種具有優化峰值粗糙度以提高二次電池的電容量保留率的電解銅箔、包含其的電極、包含其的二次電池、及其製造方法。The present invention relates to an electrolytic copper foil having an optimized peak roughness to improve the capacity retention rate of a secondary battery, an electrode including the same, a secondary battery including the same, and a manufacturing method thereof.

二次電池是一種能量轉換裝置的類型，用來將電能轉換至化學能，並儲存化學能，以及當需要電力時，藉由將化學能轉換成電能的方式產生電力，並被用作電動車輛以及行動電話、筆記型電腦等便攜式設備的能源。A secondary battery is a type of energy conversion device that converts electrical energy into chemical energy and stores chemical energy, and generates electricity by converting chemical energy into electrical energy when electricity is needed, and is used as an electric vehicle And energy for portable devices such as mobile phones and laptops.

和一次性電池相比，鉛酸電池、鎘鎘二次電池、鎳氫二次電池、鋰電池及類似的二次電池在經濟上和環境上都是較優越的。Compared with disposable batteries, lead-acid batteries, cadmium-cadmium secondary batteries, nickel-metal hydride secondary batteries, lithium batteries, and similar secondary batteries are all economically and environmentally superior.

相對於其他的二次電池之大小和重量，鋰電池可儲存相當大的電量。在信息通信設備的領域中可攜性和流動性是重要的因素，因此鋰電池是較佳的選擇，其應用範圍也擴大到用於複合車和電動車的能量貯存裝置。Compared with the size and weight of other secondary batteries, lithium batteries can store a considerable amount of power. In the field of information and communication equipment, portability and mobility are important factors, so lithium batteries are a better choice, and their application range has also been expanded to energy storage devices for hybrid vehicles and electric vehicles.

藉由重覆進行充放電的循環來使用鋰電池。當操作搭載有充滿電量之鋰電池的某一裝置時，鋰電池應有夠高的充放電容量以增加該裝置之操作時間。因此，滿足消費者對鋰電池充放電容量增加的期望是一個持續不斷的需求。Lithium batteries are used by repeating the cycle of charge and discharge. When operating a device equipped with a fully charged lithium battery, the lithium battery should have a sufficiently high charge and discharge capacity to increase the operating time of the device. Therefore, meeting consumer expectations for increased charge and discharge capacity of lithium batteries is a constant demand.

一種增加鋰電池的電容量的方法，方法提出在製造二次電池的陽極時，使用矽或錫添加到碳活性材料的複合活性材料中作為活性材料。然而，由於鋰電池的充放電而產生的熱，這種複合活性材料快速而顯著地膨脹，導致電解銅箔破裂。隨著鋰二次電池的充放電反復進行，負極活性物質交替收縮擴張。這導致銅箔與負極活性材料分離，從而降低了鋰二次電池的充電和放電電容量保留率。這種電解銅箔特別容易發生捲曲或起皺，並且電解銅箔的捲曲或起皺不僅使電解銅箔的加工困難，也使得使用者無法用活性材料塗佈電解銅箔。具體而言，由於銅箔與負極活性材料之間的黏附強度降低，所以鋰二次電池的充放電的電容量保留率顯著降低。A method for increasing the capacity of a lithium battery. The method proposes that when manufacturing an anode of a secondary battery, silicon or tin is added to a composite active material of a carbon active material as an active material. However, due to the heat generated by the charge and discharge of lithium batteries, this composite active material expands rapidly and significantly, causing the electrolytic copper foil to crack. As the charge and discharge of the lithium secondary battery are repeated, the negative electrode active materials alternately contract and expand. This results in separation of the copper foil from the negative electrode active material, thereby reducing the charge and discharge capacity retention rate of the lithium secondary battery. This electrolytic copper foil is particularly prone to curling or wrinkling, and the curling or wrinkling of the electrolytic copper foil not only makes the processing of the electrolytic copper foil difficult, but also prevents the user from coating the electrolytic copper foil with an active material. Specifically, since the adhesion strength between the copper foil and the negative electrode active material is reduced, the charge retention rate of the lithium secondary battery is significantly reduced.

當二次電池的充電和放電容量由於充放電循環的重複而迅速降低（即，當二次電池的電容量保留率低或其壽命短）時，消費者需要經常更換二次電池，造成消費者不便，並且浪費資源。When the charging and discharging capacity of a secondary battery decreases rapidly due to the repetition of the charge and discharge cycle (that is, when the capacity retention rate of the secondary battery is low or its life is short), consumers need to replace the secondary battery frequently, causing consumers Inconvenience and waste of resources.

為了增加鋰二次電池的容量，用於製造陽極的電解銅箔的厚度需要薄。然而，隨著電解銅箔的厚度減小，電解銅箔更容易捲曲或起皺。電解銅箔的捲曲或起皺不僅降低了工作性，而且使得電解銅箔不能用活性材料塗佈。In order to increase the capacity of the lithium secondary battery, the thickness of the electrolytic copper foil used for manufacturing the anode needs to be thin. However, as the thickness of the electrolytic copper foil is reduced, the electrolytic copper foil is more likely to curl or wrinkle. The curling or wrinkling of the electrolytic copper foil not only reduces workability, but also prevents the electrolytic copper foil from being coated with an active material.

本發明涉及提供一種電解銅箔、一種包含其之電極、一種包含其之二次電池、以及一種電解銅箔之製造方法，可避免先前技術的限制和缺點。The invention relates to providing an electrolytic copper foil, an electrode including the same, a secondary battery including the same, and a method for manufacturing the electrolytic copper foil, which can avoid the limitations and disadvantages of the prior art.

本發明涉及提供一種電解銅箔，此電解銅箔可確保二次電池有高電容量保留率。The invention relates to providing an electrolytic copper foil, which can ensure a high capacity retention rate of a secondary battery.

本發明涉及提供一種電極，此電極可確保二次電池有高電容量保留率。The invention relates to providing an electrode which can ensure a high capacity retention rate of a secondary battery.

本發明涉及提供一種有高電容量保留率的二次電池。The present invention relates to providing a secondary battery having a high capacity retention rate.

本發明涉及提供一種可確保二次電池有高電容量保留率的電解銅箔之製造方法。The invention relates to a method for manufacturing an electrolytic copper foil capable of ensuring a high capacity retention rate of a secondary battery.

除了本發明的上述方面外，本發明的其他特徵和優點描述如下；或者根據以下之描述，本發明的某些未描述的特徵和優點對於所屬技術領域之人員而言是可思及的。In addition to the above aspects of the present invention, other features and advantages of the present invention are described below; or, according to the following description, certain undescribed features and advantages of the present invention are conceivable to those skilled in the art.

本發明之一方面係提供一種電解銅箔，電解銅箔可以包含一第一表面、和相對於第一表面之一第二表面、一銅層、和一第一保護層，銅層包含面向第一表面之一無光澤面和面向第二表面之一光澤面；第一保護層置於銅層之無光澤面上，以及一第二保護層，置於該光澤面上；其中該第一表面和該第二表面的峰值粗糙度(Rp)的範圍為0.36μm至1.69 μm；以及該第一表面和該第二表面之峰值粗糙度的差值小於或等於0.6 μm。An aspect of the present invention is to provide an electrolytic copper foil. The electrolytic copper foil may include a first surface, a second surface opposite to the first surface, a copper layer, and a first protective layer. A matte surface on one surface and a matte surface facing the second surface; a first protective layer on the matte surface of the copper layer, and a second protective layer on the glossy surface; wherein the first surface The range of the peak roughness (Rp) from the second surface is 0.36 μm to 1.69 μm; and the difference between the peak roughness of the first surface and the second surface is less than or equal to 0.6 μm.

該第一保護層和該第二保護層可以含鉻(Cr)；以及該第一表面和該第二表面之鉻附著量的範圍可以為0.5 mg/m2 至5.5 mg/m2 。The first protective layer and the second protective layer may contain chromium (Cr); and the chromium adhesion amount of the first surface and the second surface may range from 0.5 mg / m 2 to 5.5 mg / m 2 .

該第一表面和該第二表面之鉻(Cr)附著量的差值可以小於或等於2.5 mg/m2 。The difference in the amount of chromium (Cr) adhesion between the first surface and the second surface may be less than or equal to 2.5 mg / m 2 .

該第一表面和該第二表面之表面粗糙度(Rz )可以小於或等於2.5 μm。The surface roughness (R z ) of the first surface and the second surface may be less than or equal to 2.5 μm.

在25±15℃的室溫下，該電解銅箔的降伏強度（yield strength）的範圍可以為21 kgf/mm2 至 58 kgf/mm2 。At a room temperature of 25 ± 15 ° C, the yield strength of the electrolytic copper foil may range from 21 kgf / mm 2 to 58 kgf / mm 2 .

該電解銅箔的厚度為4μm至30 μm。The thickness of this electrolytic copper foil is 4 μm to 30 μm.

本發明之另一方面係提供一種二次電池電極，二次電池電極包含一電解銅箔，包含一第一表面、和相對第一表面之一第二表面；以及一第一活性材料層，第一活性材料層在第一表面上，其中電解銅箔包含具有面向第一表面之一無光澤面和面向第二表面之一光澤面的一銅層、在銅層之無光澤面上的一第一保護層以及在該光澤面上的第二保護層，其中該第一表面和該第二表面的峰值粗糙度(Rp)的範圍為0.36μm至1.69 μm；以及該第一表面和該第二表面之峰值粗糙度的差值小於或等於0.6 μm。Another aspect of the present invention is to provide a secondary battery electrode including an electrolytic copper foil including a first surface and a second surface opposite to the first surface; and a first active material layer, the first An active material layer is on the first surface, wherein the electrolytic copper foil includes a copper layer having a matte surface facing the first surface and a glossy surface facing the second surface, and a first layer on the matte surface of the copper layer. A protective layer and a second protective layer on the glossy surface, wherein the peak roughness (Rp) of the first surface and the second surface ranges from 0.36 μm to 1.69 μm; and the first surface and the second surface The difference in peak roughness of the surface is less than or equal to 0.6 μm.

該第一保護層和該第二保護層可以含鉻(Cr)；該第一表面和該第二表面之鉻附著量的範圍可以為0.5 mg/m2 至5.5 mg/m2 ；以及該第一表面和該第二表面之鉻附著量的差值可以小於或等於2.5 mg/m2 。The first protective layer and the second protective layer may contain chromium (Cr); the chromium adhesion amount of the first surface and the second surface may range from 0.5 mg / m 2 to 5.5 mg / m 2 ; and The difference between the chromium adhesion amount of one surface and the second surface may be less than or equal to 2.5 mg / m 2 .

在25±15℃的室溫下，該電解銅箔的降伏強度（yield strength）的範圍可以為21 kgf/mm2 至 58 kgf/mm2 。At a room temperature of 25 ± 15 ° C, the yield strength of the electrolytic copper foil may range from 21 kgf / mm 2 to 58 kgf / mm 2 .

二次電池電極更包含設置在該第二表面上之一第二活性材料層；其中該第一活性材料層和該第二活性材料層包含至少一活性材料，該至少一活性材料選自碳、如矽、鍺、錫、鋰、鋅、鎂、鎘、鈰、鎳、或鐵的金屬或包含該金屬之合金、該金屬的氧化物、以及由該金屬和碳的組成物所組成的群組。The secondary battery electrode further includes a second active material layer disposed on the second surface; wherein the first active material layer and the second active material layer include at least one active material, and the at least one active material is selected from carbon, Metals such as silicon, germanium, tin, lithium, zinc, magnesium, cadmium, cerium, nickel, or iron, or alloys containing the metal, oxides of the metal, and groups consisting of the metal and carbon composition .

本發明的另外一方面係提供一種二次電池，二次電池包含一陰極、包含如請求項7至10中任一項所述的二次電池電極的一陽極、一電解質以及一隔離膜，電解質配置成可提供一環境，且鋰離子在該環境中可於陰極和陽極之間移動，隔離膜配置成可使陽極與陰極電性絕緣。Another aspect of the present invention is to provide a secondary battery including a cathode, an anode including the secondary battery electrode according to any one of claims 7 to 10, an electrolyte, and a separator, and an electrolyte. It is configured to provide an environment, and lithium ions can move between the cathode and the anode in the environment, and the isolation film is configured to electrically insulate the anode from the cathode.

本發明的另一方面係提供一種一二次電池的電解銅箔的製造方法，方法包含形成一銅層，以及在銅層上形成一保護層，其中形成該銅層之步驟包含製備一電解液，電解液包含50g/L至100g/L的銅離子、50g/L至150g/L的硫酸、3 ppm至12 ppm 的二（3-磺丙基）二硫化物 （bis-（3-sulfopropyl） disulfide，SPS），以及等於或小於50 ppm的氯；以及透過在該電解液中彼此間隔開的一電極板和一旋轉電極鼓（rotating electrode drum）在一電流密度為40A/dm2 至80A/dm2 的電流來進行電鍍；其中在該電鍍的步驟進行時，該電解液中的總碳量維持在小於或等於0.25 g/L，且鈧（Sc）和釔（Y）的總濃度維持在小於或等於350mg/L；以及使用粒徑（grit size）為800號至1500號之一拋光刷拋光該旋轉電極鼓的一表面。Another aspect of the present invention is to provide a method for manufacturing an electrolytic copper foil for a secondary battery. The method includes forming a copper layer and forming a protective layer on the copper layer. The step of forming the copper layer includes preparing an electrolyte. The electrolyte contains 50g / L to 100g / L of copper ions, 50g / L to 150g / L of sulfuric acid, and 3 ppm to 12 ppm of bis- (3-sulfopropyl) disulfide (bis- (3-sulfopropyl) disulfide (SPS), and 50 ppm or less of chlorine; and an electrode plate and a rotating electrode drum spaced apart from each other in the electrolyte at a current density of 40 A / dm 2 to 80 A / dm 2 current for electroplating; during the electroplating step, the total carbon content in the electrolyte is maintained at 0.25 g / L or less, and the total concentration of scandium (Sc) and yttrium (Y) is maintained at Less than or equal to 350 mg / L; and polishing a surface of the rotary electrode drum with a polishing brush having a grit size of 800 to 1500.

製備該電解液的步驟可以包含在600°C至900°C的溫度範圍對一銅線進行熱處理30分鐘至60分鐘；酸洗熱處理過的該銅線；向該硫酸中置入酸洗過的該銅線。The step of preparing the electrolytic solution may include heat treating a copper wire at a temperature range of 600 ° C to 900 ° C for 30 minutes to 60 minutes; pickling the heat-treated copper wire; and placing the acid-washed copper wire into the sulfuric acid. The copper wire.

形成該銅層的步驟可以更包含在進行電鍍的步驟時將過氧化氫和空氣注入該電解液中。The step of forming the copper layer may further include injecting hydrogen peroxide and air into the electrolytic solution during the step of performing electroplating.

該電解液可以更包含至少一有機添加劑，該有機添加劑係選自羥乙基纖維素（hydroxyethyl cellulose．HEC）、有機硫化物、有機氮化物、乙二醇基聚合物和硫脲類化合物所組成的群組。The electrolyte may further include at least one organic additive. The organic additive is selected from the group consisting of hydroxyethyl cellulose (HEC), organic sulfides, organic nitrides, ethylene glycol-based polymers, and thiourea compounds. Group.

形成該保護層的步驟包含將該銅層浸泡在含有0.5g/L至1.5g/L的鉻的一防鏽溶液中。The step of forming the protective layer includes immersing the copper layer in a rust-proof solution containing 0.5 g / L to 1.5 g / L of chromium.

本發明如上所述的一般性描述僅旨在說明或解釋本發明，並不用於限制本發明的範圍。The general description of the invention as described above is only intended to illustrate or explain the invention and is not intended to limit the scope of the invention.

在下文中，將參照圖式詳細描述本發明的實施例。Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

對於本發明可以進行各種修改和變更，各種修改和變更對於本領域技術人員是易於思及，且皆不脫離本發明的精神和範圍。因此，本發明包含落入所屬申請專利範圍及其均等物所限定之在本發明範圍內的所有修改和變更。Various modifications and changes can be made to the present invention, and various modifications and changes are easily conceivable by those skilled in the art without departing from the spirit and scope of the present invention. Therefore, the present invention includes all modifications and changes that fall within the scope of the present invention as defined by the scope of the patents to which they belong and their equivalents.

一種鋰離子二次電池，包含一陰極、一陽極、一電解液以及一隔離膜，電解液可提供環境讓鋰離子可於陰極和陽極之間移動，隔離膜可電性絕陰極和陽極，藉以避免二次電池的內部自其中一電極產生移動到另一電極的電子所產生不必要的消耗。A lithium ion secondary battery includes a cathode, an anode, an electrolyte, and a separator. The electrolyte provides an environment for lithium ions to move between the cathode and the anode. The separator can electrically isolate the cathode and the anode, thereby Avoid unnecessary consumption of electrons that move from one electrode to the other inside the secondary battery.

圖1係根據本發明實施例之一二次電池電極的剖面圖。FIG. 1 is a cross-sectional view of a secondary battery electrode according to an embodiment of the present invention.

如圖1所示，本發明實施例之二次電池電極100包含：一電解銅箔110，電解銅箔110包含一第一表面S1與相對於第一表面S1之一第二表面S2；設置於第一表面S1上之一第一活性材料層120a；以及設置於第二表面S2之一第二活性材料層120b。在圖1之一實施例中，第一活性材料層120a和第二活性材料層120b是分別形成在電解銅箔110的第一表面S1和第二表面S2上，不過本發明不限於此。在部分實施例中，本發明的二次電池電極100可僅包含第一活性材料層120a和第二活性材料層120b的其中一者以作為活性材料層。As shown in FIG. 1, the secondary battery electrode 100 according to the embodiment of the present invention includes: an electrolytic copper foil 110, the electrolytic copper foil 110 includes a first surface S1 and a second surface S2 opposite to the first surface S1; A first active material layer 120a on the first surface S1; and a second active material layer 120b provided on the second surface S2. In one embodiment of FIG. 1, the first active material layer 120 a and the second active material layer 120 b are respectively formed on the first surface S1 and the second surface S2 of the electrolytic copper foil 110, but the present invention is not limited thereto. In some embodiments, the secondary battery electrode 100 of the present invention may include only one of the first active material layer 120a and the second active material layer 120b as the active material layer.

通常，在一個鋰二次電池中，會用鋁箔作為正極(陰極)集電器，正極集電器連接到正極(陰極)活性材料，且會將電解銅箔作為負極(陽極)集電器，負極集電器連接到負極(陽極)活性材料。Generally, in a lithium secondary battery, aluminum foil is used as a positive electrode (cathode) current collector, the positive electrode current collector is connected to a positive electrode (cathode) active material, and electrolytic copper foil is used as a negative electrode (anode) current collector. Connected to the negative (anode) active material.

根據本發明的一實施例，二次電池電極100作為鋰二次電池的陽極，其電解銅箔110作為負極（或稱陽極）集電器來使用，而且第一活性材料層120a和第二活性材料層120b各包含負極（陽極）活性材料。According to an embodiment of the present invention, the secondary battery electrode 100 is used as an anode of a lithium secondary battery, and its electrolytic copper foil 110 is used as a negative electrode (or anode) current collector, and the first active material layer 120a and the second active material are used. The layers 120b each include a negative electrode (anode) active material.

如圖1所示，本發明的電解銅箔110包含一銅層111、一第一保護層112a、以及一第二保護層112b。銅層111包含一無光澤面MS和一光澤面SS，第一保護層112a在銅層111之無光澤面MS上，第二保護層112b在銅層111之光澤面SS上。As shown in FIG. 1, the electrolytic copper foil 110 of the present invention includes a copper layer 111, a first protective layer 112a, and a second protective layer 112b. The copper layer 111 includes a matte surface MS and a glossy surface SS. The first protective layer 112a is on the matte surface MS of the copper layer 111, and the second protective layer 112b is on the matte surface SS of the copper layer 111.

無光澤面MS為銅層111上朝向電解銅箔110的第一表面S1的表面，以及光澤面SS為銅層111上朝向電解銅箔110的第二表面S2的表面。The matte surface MS is a surface of the copper layer 111 that faces the first surface S1 of the electrolytic copper foil 110, and the matte surface SS is a surface of the copper layer 111 that faces the second surface S2 of the electrolytic copper foil 110.

本發明之銅層111可藉由電鍍形成於一旋轉電極鼓（rotating electrode drum）上。光澤面SS指的是在電鍍過程中與旋轉電極鼓接觸的表面，並且無光澤面MS是指與光澤面SS相對的表面。The copper layer 111 of the present invention can be formed on a rotating electrode drum by electroplating. The glossy surface SS refers to a surface that comes into contact with the rotating electrode drum during the plating process, and the matte surface MS refers to a surface opposite to the glossy surface SS.

通常，相較於無光澤面MS，光澤面SS具有較低的表面粗糙度(Rz )，但是本發明不以此為限，且光澤面SS的表面粗糙度(Rz )可大於或等於無光澤面MS的表面粗糙度。Typically, the MS as compared to the matte side, shiny surface SS has a lower surface roughness (R z), but the present invention is not limited thereto, and the surface roughness of the shiny surface SS (R z) may be greater than or equal to Surface roughness of the matte surface MS.

第一保護層112a和第二保護層112b可防止銅層111的腐蝕以及可改善銅層111耐熱性，且可含鉻（Cr）。The first protective layer 112a and the second protective layer 112b may prevent corrosion of the copper layer 111 and may improve heat resistance of the copper layer 111, and may contain chromium (Cr).

本發明之的電解銅箔110在室溫（25°C ± 15°C）的降伏強度（Yield Strength）可為21 kgf/mm2 至58kgf/mm2 。降伏強度藉由一萬能試驗機（universal testing machine，UTM）來測量。在此情況中，樣品的寬度為12.7mm，夾具之間的距離為50mm，測量速度為50mm/min。The yield strength of the electrolytic copper foil 110 of the present invention at room temperature (25 ° C ± 15 ° C) may be 21 kgf / mm 2 to 58 kgf / mm 2 . The undulation strength is measured by a universal testing machine (UTM). In this case, the width of the sample is 12.7 mm, the distance between the clamps is 50 mm, and the measurement speed is 50 mm / min.

當電解銅箔110的降伏強度小於21 kgf/mm2 時，電解銅箔110會有因在製造二次電池電極100和二次電池的過程中所施加的力而有折疊和/或起皺的風險。另一方面，當電解銅箔110的降伏強度大於58 kgf/mm2 時，會降低二次電池的製造過程中的工作性。When the drop strength of the electrolytic copper foil 110 is less than 21 kgf / mm 2 , the electrolytic copper foil 110 may be folded and / or wrinkled due to the force applied during the manufacturing of the secondary battery electrode 100 and the secondary battery. risk. On the other hand, when the drop-out strength of the electrolytic copper foil 110 is more than 58 kgf / mm 2 , the workability in the manufacturing process of the secondary battery is reduced.

本發明的電解銅箔110在室溫（25 °C ± 15 °C）的伸長率（Elongation）大於或等於3%。當電解銅箔110的伸長率小於3%時，製造二次電池電極100和二次電池的過程中施加的力可能無法拉伸電解銅箔110，並且增加了電解銅箔110撕裂的風險。The elongation of the electrolytic copper foil 110 of the present invention at room temperature (25 ° C ± 15 ° C) is greater than or equal to 3%. When the elongation of the electrolytic copper foil 110 is less than 3%, the force applied during the manufacturing of the secondary battery electrode 100 and the secondary battery may not be able to stretch the electrolytic copper foil 110 and increase the risk of the electrolytic copper foil 110 tearing.

本發明之電解銅箔110之厚度可為4μm至30μm。The thickness of the electrolytic copper foil 110 of the present invention may be 4 μm to 30 μm.

第一活性材料層120a和第二活性材料層120b可各包含作為負極活性材料的至少一活性材料，活性材料選自如碳、如矽、鍺、錫、鋰、鋅、鎂、鎘、鈰、鎳、或鐵之金屬、該金屬之合金、該金屬的氧化物、該金屬和碳的組成物所組成的群組。The first active material layer 120a and the second active material layer 120b may each include at least one active material as a negative electrode active material. The active material is selected from, for example, carbon, such as silicon, germanium, tin, lithium, zinc, magnesium, cadmium, cerium, and nickel. Or a group of metal of iron, alloy of metal, oxide of metal, composition of metal and carbon.

為了增加二次電池的充放電容量，第一活性材料層120a和第二活性材料層120b可由定量之矽的混合物所構成。In order to increase the charge and discharge capacity of the secondary battery, the first active material layer 120a and the second active material layer 120b may be composed of a mixture of a predetermined amount of silicon.

同時，隨著二次電池被重複充電和放電，第一活性材料層120a和第二活性材料層120b交替發生收縮和膨脹。這導致第一活性材料層120a和第二活性材料層120b與電解銅箔110分離，由此降低二次電池的充電和放電效率。因此，為了使二次電池具有電容量保持率和一定水平或更高的壽命（即，為了抑制二次電池的充電和放電效率的惡化），電解銅箔110應該對活性材料具有優異的塗佈特性，使得電解銅箔110與第一活性材料層120a和第二活性材料層120b之間的黏合強度高。At the same time, as the secondary battery is repeatedly charged and discharged, the first active material layer 120a and the second active material layer 120b alternately shrink and expand. This causes the first active material layer 120a and the second active material layer 120b to be separated from the electrolytic copper foil 110, thereby reducing the charging and discharging efficiency of the secondary battery. Therefore, in order for the secondary battery to have a capacity retention rate and a certain level or higher life (that is, to suppress deterioration of the charging and discharging efficiency of the secondary battery), the electrolytic copper foil 110 should have excellent coating of the active material. The characteristics make the adhesion strength between the electrolytic copper foil 110 and the first active material layer 120a and the second active material layer 120b high.

通常，已知通過控制電解銅箔110的表面粗糙度（Rz ）可以提高電解銅箔110與第一活性材料層120a和第二活性材料層120b之間的黏附強度。根據日本工業標準（JIS） B 0601-1994，藉由使用由Mahr製造的Mahrsurf M300照度計，測量表面粗糙度Rz （測量長度：4mm（不包括切斷部分））。Typically, it is known to improve the adhesion strength between the electrodeposited copper foil 110 and the first active material layer 120a and the second active material layer 120b by controlling the electrolytic copper foil surface roughness (R z) 110 a. According to Japanese Industrial Standard (JIS) B 0601-1994, by using an illuminometer Mahrsurf M300 manufactured by Mahr measured surface roughness R z (measured length: 4mm (not including the cut-off portion)).

根據本發明的實施例，電解銅箔110的第一表面S1和電解銅箔110的第二表面S2的表面粗糙度Rz 的範圍各可為等於或小於2.5㎛。當表面粗糙度Rz 於2.5㎛時，電解銅箔110的第一表面S1和第二表面S2會很不均勻而使得負極活性材料的塗層均勻性降低，並顯著降低電解銅箔110與第一活性材料層120a和第二活性材料層120b之間的附著力。According to an embodiment of the present invention, the ranges of the surface roughness R z of the first surface S1 of the electrolytic copper foil 110 and the second surface S2 of the electrolytic copper foil 110 may each be equal to or less than 2.5 ㎛. When the surface roughness R z is 2.5 ，, the first surface S1 and the second surface S2 of the electrolytic copper foil 110 are very uneven, which reduces the uniformity of the coating of the negative electrode active material, and significantly reduces the electrolytic copper foil 110 and the first Adhesion between an active material layer 120a and a second active material layer 120b.

然而，電解銅箔110之表面粗糙度(Rz)可適當調整，電解銅箔110分別與第一活性材料層120a和第二活性材料層120b之間的附著強度不一定會滿足一個行業規範中所要求的。即，表面粗糙度（Rz）為2.5μm以下的電解銅箔110不一定能夠確保在業內所需的二次電池（充放電500次後）有90％以上的電容量保留率。However, the surface roughness (Rz) of the electrolytic copper foil 110 can be appropriately adjusted, and the adhesion strength between the electrolytic copper foil 110 and the first active material layer 120a and the second active material layer 120b may not meet the requirements of an industry specification. required. That is, the electrolytic copper foil 110 having a surface roughness (Rz) of 2.5 μm or less does not necessarily ensure a capacity retention rate of 90% or more for a secondary battery (after 500 charge / discharge) required in the industry.

具體而言，已知的是，當第一活性材料層120a和第二活性材料層120b因含矽(Si)以增加二次電池的容量時，電解銅箔110的表面粗糙度（Rz）與二次電池的電容量保留率之間的關係較低。Specifically, it is known that when the first active material layer 120a and the second active material layer 120b contain silicon (Si) to increase the capacity of the secondary battery, the surface roughness (Rz) of the electrolytic copper foil 110 is less than The relationship between the capacity retention rates of the secondary batteries is low.

根據本發明，發現要確保電解銅箔110分別與第一活性材料層120a和第二活性材料層120b的之間有足夠的附著力以使二次電池的電容量保留率大於或等於90％，除了電解銅箔110表面的表面粗糙度(Rz)之外，電解銅箔110的峰值粗糙度(Rp)是更重要的因素。According to the present invention, it is found that to ensure sufficient adhesion between the electrolytic copper foil 110 and the first active material layer 120a and the second active material layer 120b, respectively, so that the capacity retention rate of the secondary battery is greater than or equal to 90%, In addition to the surface roughness (Rz) of the surface of the electrolytic copper foil 110, the peak roughness (Rp) of the electrolytic copper foil 110 is a more important factor.

在下文中，將參考圖2詳細描述電解銅箔110的峰值粗糙度(Rp)。Hereinafter, the peak roughness (Rp) of the electrolytic copper foil 110 will be described in detail with reference to FIG. 2.

在本發明中，峰值粗糙度（Rp）是根據JIS B 0601（2001）標準所測量，且是指自表面粗糙度分佈中的平均線的最高峰的高度（樣品長度 ：4毫米），如圖2的表面粗糙度剖面圖所示。In the present invention, the peak roughness (Rp) is measured according to JIS B 0601 (2001) and refers to the height of the highest peak from the average line in the surface roughness distribution (sample length: 4 mm), as shown in the figure. The surface roughness profile of 2 is shown.

根據本發明的一個實施例，電解銅箔110的第一表面S1和第二表面S2的峰值粗糙度(Rp)的範圍各為0.36μm至1.69 μm，且第一表面S1和第二表面S2之峰值粗糙度(Rp)的差值小於或等於0.6 μm。According to an embodiment of the present invention, the range of the peak roughness (Rp) of the first surface S1 and the second surface S2 of the electrolytic copper foil 110 is 0.36 μm to 1.69 μm, respectively, and between the first surface S1 and the second surface S2. The difference in peak roughness (Rp) is less than or equal to 0.6 μm.

當第一表面S1和第二表面S2之峰值粗糙度 (Rp)小於或等於0.36 μm時，電解銅箔110之活性比表面積(active specific surface area)可與負極活性材料的接觸太小而不能確保電解銅箔110與第一活性材料層120a和第二活性材料層120b之間有足夠的附著力。另一方面，當第一表面S1和第二表面S2之峰值粗糙度(Rp)大於1.69 μm時，負極活性材料的塗佈均勻性降低，因此電解銅箔110與第一活性材料層120a和第二活性材料層120b之間的附著力明顯降低。在二次電池的充放電時，應力集中在超過1.69μm的峰值，使得負極活性材料與電解銅箔110分離，導致二次電池的電容量保留率降低。When the peak roughness (Rp) of the first surface S1 and the second surface S2 is less than or equal to 0.36 μm, the active specific surface area of the electrolytic copper foil 110 may be too small to ensure contact with the negative electrode active material. There is sufficient adhesion between the electrolytic copper foil 110 and the first active material layer 120a and the second active material layer 120b. On the other hand, when the peak roughness (Rp) of the first surface S1 and the second surface S2 is greater than 1.69 μm, the coating uniformity of the negative electrode active material is reduced, so the electrolytic copper foil 110 and the first active material layer 120a and The adhesion between the two active material layers 120b is significantly reduced. During the charging and discharging of the secondary battery, the stress is concentrated at a peak exceeding 1.69 μm, which causes the negative electrode active material to be separated from the electrolytic copper foil 110, resulting in a reduction in the capacity retention rate of the secondary battery.

當第一表面S1和第二表面S2之峰值粗糙度(Rp)的差值大於0.6 μm時，在第一表面S1和第一活性材料層120a之間以及第二表面S2和第二活性材料層120b之間的附著力之間的差異變得太大，這導致二次電池的電容量保留率下降。When the difference between the peak roughness (Rp) of the first surface S1 and the second surface S2 is greater than 0.6 μm, between the first surface S1 and the first active material layer 120a and the second surface S2 and the second active material layer The difference between the adhesion between 120b becomes too large, which causes the capacity retention rate of the secondary battery to decrease.

根據本發明，已知當確保電解銅箔110與第一活性材料層120a和第二活性材料層120b之間的黏附力時，在電解銅箔110的第一表面S1和第二表面S2上，鉻附著量也是重要的因素。鉻附著量可以通過原子吸收光譜法（atomic absorption spectormetry，AAS）分析來測量。According to the present invention, it is known that when the adhesion between the electrolytic copper foil 110 and the first active material layer 120a and the second active material layer 120b is ensured, on the first surface S1 and the second surface S2 of the electrolytic copper foil 110, The amount of chromium deposited is also an important factor. The amount of chromium deposited can be measured by atomic absorption spectrometry (AAS) analysis.

例如，將電解銅箔110的第二表面S2用膠帶遮蔽並切割得到10cm×10cm的樣品，然後將電解銅箔110的第一表面S1溶解在硝酸水溶液（正常的硝酸與水的比率一比一的混合物），同時注意不要在電解銅箔110上形成孔。得到的溶液可以用水稀釋以獲得50mL稀釋的溶液，然後可以在25℃下用AAS分析稀釋的溶液，以測量電解銅箔110的第一表面S1上的鉻附著量。可以以類似的方式測量電解銅箔110的第二表面S2上的鉻附著量。For example, the second surface S2 of the electrolytic copper foil 110 is covered with tape and cut to obtain a 10 cm × 10 cm sample, and then the first surface S1 of the electrolytic copper foil 110 is dissolved in an aqueous nitric acid solution (a normal nitric acid to water ratio of one to one Mixture), while taking care not to form holes in the electrolytic copper foil 110. The obtained solution can be diluted with water to obtain 50 mL of the diluted solution, and then the diluted solution can be analyzed by AAS at 25 ° C. to measure the amount of chromium attached on the first surface S1 of the electrolytic copper foil 110. The amount of chromium attached on the second surface S2 of the electrolytic copper foil 110 can be measured in a similar manner.

根據本發明的實施例，第一表面和第二表面的鉻附著量的範圍為0.5 mg/m2 至5.5 mg/m2 。當鉻附著量小於0.5mg/m2 時，氧穿過第一活性材料層120a和第二活性材料層120b而引起銅層111表面的氧化，結果，電解銅箔110和負極活性材料之間可能無法提供足夠的化學鍵合。另一方面，當鉻附著量大於5.5mg/m2 時，電解銅箔110表面的疏水性增加，對負極活性物質的化學親和力下降，結果，電解銅箔110和負極活性材料之間可能無法提供足夠的化學鍵合。According to an embodiment of the present invention, the chromium adhesion amount of the first surface and the second surface ranges from 0.5 mg / m 2 to 5.5 mg / m 2 . When the chromium adhesion amount is less than 0.5 mg / m 2 , oxygen passes through the first active material layer 120 a and the second active material layer 120 b and causes the surface of the copper layer 111 to be oxidized. Not providing sufficient chemical bonding. On the other hand, when the chromium adhesion amount is more than 5.5 mg / m 2 , the hydrophobicity of the surface of the electrolytic copper foil 110 increases, and the chemical affinity for the negative electrode active material decreases. As a result, the electrolytic copper foil 110 and the negative electrode active material may not be provided. Enough chemical bonding.

此外，根據本發明的一個實施例，為了將電解銅箔110的捲曲最小化而使第一表面S1和第二表面S2之間的鉻附著量的差值為2.5mg/m2 或更小，則可能會導致工作性下降。In addition, according to an embodiment of the present invention, in order to minimize the curl of the electrolytic copper foil 110, the difference in the amount of chromium adhesion between the first surface S1 and the second surface S2 is 2.5 mg / m 2 or less, May result in reduced workability.

以下，根據本發明的一實施例，將詳細描述製造電解銅箔110的方法。Hereinafter, a method of manufacturing the electrolytic copper foil 110 will be described in detail according to an embodiment of the present invention.

本發明的方法包括形成銅層111，以及在銅層111上形成第一保護層112a和第二保護層112b。The method of the present invention includes forming a copper layer 111, and forming a first protective layer 112a and a second protective layer 112b on the copper layer 111.

首先，製備含有50至100g/L的銅離子、50至150g/L的硫酸、3至12ppm的二（3-磺丙基）二硫化物（SPS）、和等於或小於50 ppm的氯的電解液。First, an electrolysis 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 chlorine of 50 ppm or less is prepared. liquid.

接下來，藉由在40℃至60℃的電解液中彼此間隔開的電極板和旋轉電極鼓(rotating electrode drum)之間產生電流密度為40至80A/dm2 的電流進行電鍍，以在旋轉電極鼓上形成銅層111。Next, electroplating is performed by generating a current with a current density of 40 to 80 A / dm 2 between an electrode plate and a rotating electrode drum spaced apart from each other in an electrolyte at 40 ° C. to 60 ° C. to rotate the A copper layer 111 is formed on the electrode drum.

根據本發明，在電鍍過程中控制電解液，使電解液中的總碳量（total carbon，TC）維持在小於或等於0.25g/L。總碳量（TC）可包含總有機碳量（total organic carbon，TOC）和總無機碳量（total inorganic carbon，TIC），並且可以通過TC測量設備進行分析。According to the present invention, the electrolytic solution is controlled during the electroplating process so that the total carbon (TC) in the electrolytic solution is maintained at 0.25 g / L or less. The total carbon content (TC) may include total organic carbon (TOC) and total inorganic carbon (TIC), and may be analyzed by a TC measurement device.

為了維持電解液的TC小於或等於0.25 g/L，對高純度銅線進行溫度為600°C至900°C之熱處理30分鐘至60分鐘以燒結有機物質，酸洗進行過熱處理之銅線，並藉由將酸洗過之銅線置入硫酸中，以製備含少量或不含雜質的電解液。In order to maintain the TC of the electrolyte less than or equal to 0.25 g / L, heat-treating high-purity copper wires at a temperature of 600 ° C to 900 ° C for 30 to 60 minutes to sinter organic substances and pickling the heat-treated copper wires And the acid-washed copper wire is put into sulfuric acid to prepare an electrolyte containing little or no impurities.

為了將電解液的總碳量（TC）維持在0.25g/L以下，可以通過臭氧處理分解電解液中的有機物質來降低總碳量（TC）。並且，通過在電鍍期間將過氧化氫和空氣注入電解液可以改善電解液的純度(purity)。In order to maintain the total carbon content (TC) of the electrolytic solution below 0.25 g / L, the organic matter in the electrolytic solution can be decomposed by ozone treatment to reduce the total carbon content (TC). Also, the purity of the electrolytic solution can be improved by injecting hydrogen peroxide and air into the electrolytic solution during plating.

根據本發明，在電鍍期間電解液中鈧（Sc）和釔（Y）的總濃度維持在小於或等於350mg/L。在電解液中，鈧（Sc）和釔（Y）各可以具有等於或大於0.1mg/L的濃度。 例如，電解液中的鈧（Sc）和釔（Y）各可以具有0.1至0.2mg/L的濃度。According to the present invention, the total concentration of scandium (Sc) and yttrium (Y) in the electrolytic solution is maintained at 350 mg / L or less during electroplating. In the electrolytic solution, scandium (Sc) and yttrium (Y) may each have a concentration equal to or greater than 0.1 mg / L. For example, thallium (Sc) and yttrium (Y) in the electrolytic solution may each have a concentration of 0.1 to 0.2 mg / L.

旋轉電極鼓的表面（例如，通過執行電鍍沉澱銅的表面）的拋光程度也是一個控制電解銅箔110的第二表面S2的表面粗糙度（Rz ）、峰值粗糙度（Rp）和鉻附著量的因素。根據本發明，使用粒徑（grit size）為800號至1500號之拋光刷拋光該旋轉電極鼓的表面。The electrode surface of the rotating drum (e.g., by performing the precipitation surface of the copper plating) is also a degree of polishing a surface roughness (R z), the peak roughness (Rp) and a chromium coating weight of the second surface S2 of the electrolytic copper foil 110 control the elements of. According to the present invention, the surface of the rotary electrode drum is polished using a polishing brush having a grit size of 800 to 1500.

旋轉電極鼓的表面使用粒徑為800號至1500號之拋光刷拋光，電解液的TC和鈧（Sc）和釔（Y）的總濃度分別維持在等於或小於0.25g/L且等於或小於350mg/L以下，施加40至80A/dm2 的電流密度，並且因此本發明的電解銅箔110的第一表面S1和第二表面S2之間的峰值粗糙度（Rp）之間的差值可以被控制在一個範圍內[峰值粗糙度（Rp）：0.36μm至1.69μm；峰值粗糙度（Rp）差值：等於或小於0.6μm]。The surface of the rotating electrode drum is polished with a polishing brush having a particle size of 800 to 1500, and the total concentration of TC, thorium (Sc) and yttrium (Y) in the electrolyte is maintained at or below 0.25 g / L and equal to or less Below 350 mg / L, a current density of 40 to 80 A / dm 2 is applied, and thus the difference between the peak roughness (Rp) between the first surface S1 and the second surface S2 of the electrolytic copper foil 110 of the present invention can be It is controlled within a range [peak roughness (Rp): 0.36 μm to 1.69 μm; peak roughness (Rp) difference: 0.6 μm or less].

在電鍍進行時，以31m3 /hr至45m3 /hr的流量進行連續過濾(Continuous Filtration或Circulating Filtration)，以從電解液中去除固體雜質。當流量小於31m3 /hr時，流速降低而電壓升高，銅層111將被不均勻地形成。另一方面，當流量大於45m3 /hr時，過濾器被損壞並且外界的異物可能被引入到電解液中，增加電解液的TC。When the electroplating is performed, continuous filtration (Continuous Filtration or Circulating Filtration) is performed at a flow rate of 31 m 3 / hr to 45 m 3 / hr to remove solid impurities from the electrolytic solution. When the flow rate is less than 31 m 3 / hr, the flow rate decreases and the voltage increases, and the copper layer 111 will be unevenly formed. On the other hand, when the flow rate is more than 45 m 3 / hr, the filter is damaged and foreign matter from the outside may be introduced into the electrolyte, increasing the TC of the electrolyte.

可選用地，電解液可進一步包含一有機添加劑，有機添加劑係選自羥乙基纖維素（hydroxyethyl cellulose．HEC）、有機硫化物、有機氮化物、乙二醇基聚合物和硫脲類化合物所組成的群組。Optionally, the electrolyte may further include an organic additive selected from the group consisting of hydroxyethyl cellulose (HEC), organic sulfides, organic nitrides, ethylene glycol-based polymers, and thiourea compounds. Group of people.

第一保護層112a和第二保護層112b通過將所得到的銅層111浸入含有0.5 g/L至1.5g/L的鉻的防鏽溶液中而形成在銅層111上（例如，在室溫下時間從2秒到20秒），然後乾燥銅層111。The first protective layer 112a and the second protective layer 112b are formed on the copper layer 111 by immersing the obtained copper layer 111 in a rust-preventing solution containing 0.5 g / L to 1.5 g / L of chromium (for example, at room temperature). Down time from 2 seconds to 20 seconds), and then the copper layer 111 is dried.

防鏽溶液還可以更包括矽烷化合物和氮化合物中的至少一者。例如防鏽溶液可以含有0.5g/L至1.5g/L的鉻和0.5g/L至1.5g/L的矽烷化合物。The antirust solution may further include at least one of a silane compound and a nitrogen compound. For example, the anti-rust solution may contain 0.5 g / L to 1.5 g / L of chromium and 0.5 g / L to 1.5 g / L of a silane compound.

本發明的二次電池電極（即，陽極）可以通過在本發明的所得電解銅箔110上塗佈負極活性材料來製造。The secondary battery electrode (that is, the anode) of the present invention can be manufactured by coating a negative electrode active material on the obtained electrolytic copper foil 110 of the present invention.

負極活性材料選自如碳、如矽、鍺、錫、鋰、鋅、鎂、鎘、鈰、鎳、或鐵的金屬、該金屬之合金、該金屬之氧化物、以及該金屬和碳的組成物所組成的群組。The anode active material is selected from metals such as carbon, metals such as silicon, germanium, tin, lithium, zinc, magnesium, cadmium, cerium, nickel, or iron, alloys of the metals, oxides of the metals, and combinations of the metals and carbon A group of people.

例如，藉由混合1至3重量比的苯乙烯-丁二烯橡膠（styrene butadiene rubber．SBR）和1至3重量比的羧甲基纖維素（carboxymethyl cellulose．CMC）以及100重量比的碳作為負極活性材料，然後使用蒸餾水作為溶劑，以製備漿料(slurry)。隨後，藉由刮刀在電解銅箔110上塗佈厚度為20μm至100μm的漿料，並在100℃至130℃的溫度下以0.5 ton/cm2 至1.5 ton/cm2 的壓力加壓。For example, by mixing 1 to 3 weight ratio of styrene butadiene rubber (SBR) and 1 to 3 weight ratio of carboxymethyl cellulose (CMC) and 100 weight ratio of carbon as A negative electrode active material, and then distilled water was used as a solvent to prepare a slurry. Subsequently, the electrolytic copper foil 110 is coated with a slurry having a thickness of 20 μm to 100 μm by a doctor blade, and pressurized at a temperature of 100 ° C. to 130 ° C. under a pressure of 0.5 ton / cm 2 to 1.5 ton / cm 2 .

鋰二次電池可以使用一傳統的陰極、一電解液和一隔膜以及如上所述所製造的二次電池電極（或陽極）來製造。The lithium secondary battery can be manufactured using a conventional cathode, an electrolyte, and a separator, and a secondary battery electrode (or anode) manufactured as described above.

以下，參照實施例和比較例詳細說明本發明之內容。然而，以下實施例僅作為幫助了解本發明的實施例，本發明的範圍不限於這些實施例。Hereinafter, the contents of the present invention will be described in detail with reference to examples and comparative examples. However, the following examples are merely examples to help understand the present invention, and the scope of the present invention is not limited to these examples.

實施例Examples 11 至to 33 和比較例And comparative example 11 至to 55

在電解液中被彼此間隔的電極板和旋轉電極鼓之間產生電流密度為50A/dm2 的電流以在旋轉電極鼓上銅層。電解液包含75g/L的銅離子、100g/L的硫酸、8ppm的SPS、和20ppm的氯離子（Cl），並維持在55°C的溫度下。用於電鍍的電流密度、SPS濃度、PEG濃度、總碳量（TC）和銀（Ag）濃度，以及用於研磨旋轉電極鼓的表面的拋光刷的粒徑如下表1所示。通過浸泡通過電鍍形成的銅層，然後乾燥銅層來完成電解銅箔。在進行電鍍時，以37m3 /hr之流量進行連續過濾，以從電解液中去除固體雜質。電解液中的乙烯三脲（ETU）含量、電解液中的TC、電解液中鈧（Sc）和釔（Y）的總濃度以及用於拋光旋轉電極鼓的表面的研磨刷的顆粒尺寸如表1所示。將進行電鍍而形成之銅層浸泡在一防鏽溶液中，然後乾燥此銅層來製備電解銅箔。A current having a current density of 50 A / dm 2 was generated between the electrode plate and the rotating electrode drum spaced apart from each other in the electrolytic solution to form a copper layer on the rotating electrode drum. The electrolyte contained 75 g / L of copper ions, 100 g / L of sulfuric acid, 8 ppm of SPS, and 20 ppm of chloride ions (Cl), and was maintained at a temperature of 55 ° C. The current density, SPS concentration, PEG concentration, total carbon content (TC) and silver (Ag) concentration used for electroplating, and the particle size of the polishing brush used for polishing the surface of the rotating electrode drum are shown in Table 1 below. The electrolytic copper foil is completed by soaking a copper layer formed by electroplating, and then drying the copper layer. During electroplating, continuous filtration was performed at a flow rate of 37 m 3 / hr to remove solid impurities from the electrolyte. The content of ethylene triurea (ETU) in the electrolyte, the TC in the electrolyte, the total concentrations of thorium (Sc) and yttrium (Y) in the electrolyte, and the particle size of the abrasive brush used to polish the surface of the rotating electrode drum are shown in the table. 1 is shown. A copper layer formed by electroplating is immersed in a rust-proof solution, and the copper layer is dried to prepare an electrolytic copper foil.

[表1] [Table 1]

在如上所述製造的實施例1至3和比較例1至5中分別獲得電解銅箔的第一表面(例如面對銅層之無光澤面的電解銅箔表面)的峰值粗糙度（Rp）以及相對於電解銅箔之第一表面的第二表面的峰值粗糙度（Rp），並且如下獲得每個電解銅箔的降伏強度（yield strength）。另外，在實施例1至3和比較例1至5中獲得由電解銅箔製成的陽極的二次電池之電容量保留率，其結果如表2所示。The peak roughness (Rp) of the first surface of the electrolytic copper foil (for example, the surface of the electrolytic copper foil facing the matte side of the copper layer) was obtained in Examples 1 to 3 and Comparative Examples 1 to 5 manufactured as described above, respectively. And the peak roughness (Rp) of the second surface with respect to the first surface of the electrolytic copper foil, and the yield strength of each electrolytic copper foil was obtained as follows. In addition, in Examples 1 to 3 and Comparative Examples 1 to 5, the capacity retention rates of the secondary batteries of anodes made of electrolytic copper foil were obtained, and the results are shown in Table 2.

峰值粗糙度 (Rp) (μm)Peak Roughness (Rp) (μm)

量測電解銅箔的第一表面和第二表面每一者上任意三點的峰值粗糙度（Rp），並且獲得其平均值。The peak roughness (Rp) of any three points on each of the first surface and the second surface of the electrolytic copper foil was measured, and the average value was obtained.

根據JIS B 0601（2001）標準，通過從表面粗糙度分佈中的平均線，測量最高峰的高度，獲得每個點處的峰值粗糙度（Rp）。在這種情況下使用的照度計是由Mitsutoyo Co.製造的SJ-310照度計。掃描速度為0.1mm/sec，一次測量的長度為4mm，探針尺寸為5μm。According to the JIS B 0601 (2001) standard, the peak roughness (Rp) at each point is obtained by measuring the height of the highest peak from the average line in the surface roughness distribution. The light meter used in this case is an SJ-310 light meter manufactured by Mitsutoyo Co. The scanning speed was 0.1 mm / sec, the length of one measurement was 4 mm, and the probe size was 5 μm.

在25±15℃的室溫下的降伏強度(kgf/mm2 )Falling strength at room temperature of 25 ± 15 ℃ (kgf / mm 2 )

使用UTM測量室溫下電解銅箔的降伏強度。在這種情況下，樣品的寬度是12.7mm，夾具之間的距離是50mm，測量速度是50mm/min。The drop strength of electrolytic copper foil at room temperature was measured using UTM. In this case, the width of the sample is 12.7mm, the distance between the clamps is 50mm, and the measurement speed is 50mm / min.

二次電池的電容量保留率 (%)Capacity retention rate of secondary battery (%)

首先，在實施例1至3和比較例1至5中用電解銅箔製備陽極。具體地說，將2重量份的SBR和2重量份的CMC混合在的100重量份之市面上可購得的碳中作為負極活性材料。然後，將使用蒸餾水作為溶劑所製備之漿料加入到混合物中。藉由使用一刮刀在電解銅箔(寬度：10cm)表上塗佈厚度為60μm的漿料，並在120°C的溫度下乾燥，接著通過在其上進行的滾壓法(壓力：1 ton/cm2 )製備陽極。First, an anode was prepared using electrolytic copper foil in Examples 1 to 3 and Comparative Examples 1 to 5. Specifically, 2 parts by weight of SBR and 2 parts by weight of CMC were mixed in 100 parts by weight of commercially available carbon as a negative electrode active material. Then, a slurry prepared using distilled water as a solvent was added to the mixture. The electrolytic copper foil (width: 10 cm) was coated with a paste having a thickness of 60 μm by using a doctor blade and dried at a temperature of 120 ° C., followed by a rolling method (pressure: 1 ton) performed thereon. / cm 2 ) to prepare an anode.

以90：10的重量比混合之鋰錳氧化物(lithium manganese oxide)和鋰錳氧化物(lithium manganese oxide)有一斜方晶體結構，並將其用來製備正電極活性材料，鋰錳氧化物例如Li1.1 Mn1.85 Al0.05 O4 ，鋰錳氧化物例如o-LiMnO2 。將正電極活性材料、碳黑和聚偏二氟乙烯(polyvinylidene fluoride．PVDF)與作為有機溶劑的N-甲基吡咯酮(N-methyl-2-pyrrolidone．NMP)以85：10：5的重量比混合以製備漿料。鋁箔的兩個表面有塗佈厚度為20μm的漿料，並乾燥以製備陰極。Lithium manganese oxide and lithium manganese oxide mixed at a weight ratio of 90:10 have an orthorhombic crystal structure and are used to prepare a positive electrode active material, such as lithium manganese oxide, for example Li 1.1 Mn 1.85 Al 0.05 O 4 , lithium manganese oxide such as o-LiMnO 2 . The weight of the positive electrode active material, carbon black, polyvinylidene fluoride (PVDF) and N-methyl-2-pyrrolidone (NMP) as an organic solvent was 85: 10: 5. Ratio to prepare a slurry. A slurry having a thickness of 20 μm was coated on both surfaces of the aluminum foil, and dried to prepare a cathode.

另外，在一無水有機溶劑中藉由將1M的六氟磷酸鋰(LiPF6 )作為溶質溶解得到鹼性電解液，其中無水有機溶劑中碳酸伸乙酯(ethylene carbonate．EC)和碳酸甲乙酯(ethyl methyl carbonate．EMC)以1：2的重量比混合。藉由混合99.5wt%的鹼性電解液和0.5wt%的琥珀酸酐(succinic anhydride)來製備一二次電池的電解液。In addition, an alkaline electrolyte was obtained by dissolving 1M lithium hexafluorophosphate (LiPF 6 ) as a solute in an anhydrous organic solvent. The anhydrous organic solvent was ethylene carbonate (EC) and ethyl methyl carbonate (ethyl methyl carbonate). carbonate.EMC) was mixed at a weight ratio of 1: 2. An electrolytic solution for a secondary battery was prepared by mixing 99.5 wt% of an alkaline electrolytic solution and 0.5 wt% of succinic anhydride.

使用陽極、陰極和如上所述所製備的電解液來製備二次電池。A secondary battery is prepared using an anode, a cathode, and an electrolytic solution prepared as described above.

接下來，對於如上所述製造的二次電池，用4.3V的充電操作電壓和3.4V的放電操作電壓測量每克陰極的電容量，在50℃的溫度下，以0.2C的充電速率進行500次充電實驗，並且根據以下方程式1計算二次電池的電容量保留率。二次電池行業所需的容量保留率為大於或等於90％。Next, for the secondary battery manufactured as described above, the electric capacity per gram of the cathode was measured with a charging operation voltage of 4.3 V and a discharging operation voltage of 3.4 V, and the temperature was 500 ° C at a charging rate of 0.2 C at a temperature of 50 ° C. Charge experiment, and calculate the capacity retention rate of the secondary battery according to Equation 1 below. The capacity retention rate required by the secondary battery industry is greater than or equal to 90%.

[方程式 1][Equation 1]

電容量保留率(%) = (第500次放電容量/第一次放電容量)x100Capacitance retention rate (%) = (500th discharge capacity / first discharge capacity) x100

對於每個電解銅箔取五個樣品，使用上述方法用五個樣品製備五個二次電池，使用上述方法測量五個二次電池中的每一個的電容量保留率，並將測量值進行數學平均以獲得與電解銅箔相對應的二次電池電容量保留率。Take five samples for each electrolytic copper foil, use the above method to prepare five secondary batteries from the five samples, use the above method to measure the capacity retention rate of each of the five secondary batteries, and mathematically measure the measured values On average, the secondary battery capacity retention rate corresponding to the electrolytic copper foil was obtained.

[表 2] [Table 2]

參考上述表2，可以看出，當電解銅箔的第一表面和第二表面的峰值粗糙度（Rp）的差值小於0.36μm（比較例1和3）時、當電解銅箔的第一表面和第二表面的峰值粗糙度（Rp）的差值大於1.69μm（比較例2和4）時、當電解銅箔的第一表面和第二表面之間的峰值粗糙度（Rp）的差值大於0.6μm（比較例5）時，二次電池的電容量保留率明顯低於工業要求的值（90％）。Referring to Table 2 above, it can be seen that when the difference between the peak roughness (Rp) of the first and second surfaces of the electrolytic copper foil is less than 0.36 μm (Comparative Examples 1 and 3), When the difference between the peak roughness (Rp) of the surface and the second surface is greater than 1.69 μm (Comparative Examples 2 and 4), the difference in peak roughness (Rp) between the first and second surfaces of the electrolytic copper foil When the value is larger than 0.6 μm (Comparative Example 5), the capacity retention rate of the secondary battery is significantly lower than the industrially required value (90%).

圖3和圖4是分別示出使用實施例1和比較例1製造的電解銅箔製造的二次電池的充放電測試後的陽極狀態的照片。3 and 4 are photographs showing the anode state after a charge-discharge test of a secondary battery manufactured using the electrolytic copper foil manufactured in Example 1 and Comparative Example 1, respectively.

如圖3所示，在由實施例1的電解銅箔製造的陽極中，即使經過500次充放電試驗，銅層和活性物質層仍保持牢固的黏附。另一方面，如圖4所示，在由比較例1的電解銅箔製造的陽極中，可以看出在500次充電和放電測試之後，活性材料層的一部分的顯著區域與銅層分離。As shown in FIG. 3, in the anode manufactured from the electrolytic copper foil of Example 1, even after 500 charge and discharge tests, the copper layer and the active material layer remained firmly adhered. On the other hand, as shown in FIG. 4, in the anode manufactured from the electrolytic copper foil of Comparative Example 1, it can be seen that a significant area of a part of the active material layer was separated from the copper layer after 500 charge and discharge tests.

根據本發明，即使重複充電和放電循環，可以製造能夠長時間保持高充放電容量的長壽命二次電池。因此，可以將由於二次電池的頻繁更換引起的電子產品的消費者不便和資源浪費的降至最低。According to the present invention, a long-life secondary battery capable of maintaining a high charge-discharge capacity for a long time can be manufactured even if the charge and discharge cycles are repeated. Therefore, consumer inconvenience and waste of resources of electronic products caused by frequent replacement of secondary batteries can be minimized.

100‧‧‧電極100‧‧‧ electrode

110‧‧‧電解銅箔110‧‧‧electrolytic copper foil

111‧‧‧銅層111‧‧‧ Copper

112a‧‧‧第一保護層112a‧‧‧First protective layer

112b‧‧‧第二保護層112b‧‧‧Second protective layer

120a‧‧‧第一活性材料層120a‧‧‧first active material layer

120b‧‧‧第二活性材料層120b‧‧‧Second active material layer

S1‧‧‧第一表面S1‧‧‧First surface

S2‧‧‧第二表面S2‧‧‧Second surface

MS‧‧‧無光澤面MS‧‧‧ Matte surface

SS‧‧‧光澤面SS‧‧‧Glossy

圖1係根據本發明實施例之一二次電池電極的剖面圖。 圖2示出了根據日本工業標準（JIS）B 0601（2001）標準獲得的表面粗糙度分佈圖。 圖3和圖4是分別示出使用實施例1和比較例1的電解銅箔製造的二次電池在充電和放電測試之後的陽極狀態的照片。FIG. 1 is a cross-sectional view of a secondary battery electrode according to an embodiment of the present invention. FIG. 2 shows a surface roughness distribution map obtained according to the Japanese Industrial Standard (JIS) B 0601 (2001) standard. 3 and 4 are photographs showing the anode states of the secondary batteries manufactured using the electrolytic copper foils of Example 1 and Comparative Example 1, respectively, after the charge and discharge tests.

Claims (16)

一種電解銅箔，包含一第一表面和相對於該第一表面之一第二表面，該電解銅箔包含： 一銅層，包含面向該第一表面之一無光澤面和面向該第二表面之一光澤面； 一第一保護層，在該無光澤面上；以及 一第二保護層，在該光澤面上； 其中： 該第一表面和該第二表面的峰值粗糙度(Rp)的範圍為0.36μm至1.69 μm；以及 該第一表面和該第二表面之峰值粗糙度的差值小於或等於0.6μm。An electrolytic copper foil includes a first surface and a second surface opposite to the first surface. The electrolytic copper foil includes: a copper layer including a matte surface facing the first surface and facing the second surface A glossy surface; a first protective layer on the matte surface; and a second protective layer on the glossy surface; wherein: the peak roughness (Rp) of the first surface and the second surface The range is 0.36 μm to 1.69 μm; and the difference between the peak roughness of the first surface and the second surface is less than or equal to 0.6 μm. 如請求項1之電解銅箔，其中 該第一保護層和該第二保護層含鉻(Cr)；以及 該第一表面和該第二表面之一鉻(Cr)附著量的範圍為0.5 mg/m2 至5.5 mg/m2 。The electrolytic copper foil of claim 1, wherein the first protective layer and the second protective layer contain chromium (Cr); and the amount of chromium (Cr) attached to one of the first surface and the second surface ranges from 0.5 mg / m 2 to 5.5 mg / m 2 . 如請求項2之電解銅箔，其中該第一表面和該第二表面之鉻附著量的差值小於或等於2.5 mg/m2 。For example, the electrolytic copper foil of claim 2, wherein the difference between the chromium adhesion amount of the first surface and the second surface is less than or equal to 2.5 mg / m 2 . 如請求項1之電解銅箔，其中該第一表面和該第二表面之表面粗糙度(Rz )小於或等於2.5μm。The electrolytic copper foil of claim 1, wherein the surface roughness (R z ) of the first surface and the second surface is less than or equal to 2.5 μm. 如請求項1之電解銅箔，其中在25±15℃的室溫下，該電解銅箔的降伏強度（yield strength）的範圍為21 kgf/mm2 至 58 kgf/mm2 。For example, the electrolytic copper foil of claim 1, wherein at room temperature of 25 ± 15 ° C, the yield strength of the electrolytic copper foil ranges from 21 kgf / mm 2 to 58 kgf / mm 2 . 如請求項1之電解銅箔，其中該電解銅箔的厚度為4μm至30 μm。The electrolytic copper foil of claim 1, wherein the thickness of the electrolytic copper foil is 4 μm to 30 μm. 一種二次電池電極，包含： 一電解銅箔，包含一第一表面和相對該第一表面之一第二表面；以及 一第一活性材料層，在該第一表面上； 其中： 該電解銅箔包含： 一銅層，包含面向該第一表面之一無光澤面和面向該第二表面之一光澤面； 一第一保護層，在該無光澤面上；以及 一第二保護層，在該光澤面上； 該第一表面和該第二表面的峰值粗糙度(Rp)的範圍為0.36μm至1.69 μm；以及 該第一表面和該第二表面之峰值粗糙度的差值小於或等於0.6 μm。A secondary battery electrode includes: an electrolytic copper foil including 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 The foil includes: a copper layer including a matte surface facing the first surface and a glossy surface facing the second surface; a first protective layer on the matte surface; and a second protective layer on the The glossy surface; the peak roughness (Rp) of the first surface and the second surface ranges from 0.36 μm to 1.69 μm; and the difference between the peak roughness of the first surface and the second surface is less than or equal to 0.6 μm. 如請求項7之二次電池電極，其中： 該第一保護層和該第二保護層含鉻(Cr)； 該第一表面和該第二表面之鉻附著量的範圍為0.5mg/m2 至5.5mg/m2 ；以及 該第一表面和該第二表面之鉻附著量的差值小於或等於2.5 mg/m2 。The secondary battery electrode of claim 7, wherein: the first protective layer and the second protective layer contain chromium (Cr); and the chromium adhesion amount of the first surface and the second surface ranges from 0.5 mg / m 2 To 5.5 mg / m 2 ; and the difference in the amount of chromium attached to the first surface and the second surface is less than or equal to 2.5 mg / m 2 . 如請求項7之二次電池電極，其中在25±15℃的室溫下，該電解銅箔的降伏強度（yield strength）的範圍為21 kgf/mm2 至58 kgf/mm2 。For example, the secondary battery electrode of claim 7, wherein the yield strength of the electrolytic copper foil ranges from 21 kgf / mm 2 to 58 kgf / mm 2 at a room temperature of 25 ± 15 ° C. 如請求項7之二次電池電極，更包含設置在該第二表面上之一第二活性材料層； 其中該第一活性材料層和該第二活性材料層包含至少一活性材料，該至少一活性材料選自碳、如矽、鍺、錫、鋰、鋅、鎂、鎘、鈰、鎳、或鐵的金屬或包含該金屬之合金、該金屬的氧化物、以及由該金屬和碳的組成物所組成的群組。The secondary battery electrode of claim 7, further comprising a second active material layer disposed on the second surface; wherein the first active material layer and the second active material layer include at least one active material, and the at least one The active material is selected from carbon, a metal such as silicon, germanium, tin, lithium, zinc, magnesium, cadmium, cerium, nickel, or iron, or an alloy containing the metal, an oxide of the metal, and a composition consisting of the metal and carbon A group of things. 一種二次電池，包含： 一陰極； 一陽極，包含如請求項7至10中任一項所述的該二次電池電極； 一電解液，用以提供讓鋰離子可在該陰極和該陽極之間移動的環境；以及 一隔離膜，用以電性絕緣該陰極和該陽極。A secondary battery including: a cathode; an anode including the secondary battery electrode according to any one of claims 7 to 10; an electrolyte for providing lithium ions to the cathode and the anode A moving environment; and an isolation film for electrically insulating the cathode and the anode. 一種電解銅箔的製造方法，該方法包含： 形成一銅層；以及 形成一保護層於該銅層上； 其中： 形成該銅層之步驟包含： 製備一電解液，該電解液包含50g/L至100g/L的銅離子、50g/L至150g/L的硫酸、3ppm至12ppm的二（3-磺丙基）二硫化物（bis-（3-sulfopropyl） disulfide，SPS）、以及等於或小於50 ppm的氯；以及 透過該電解液中彼此間隔開的一電極板和一旋轉電極鼓（rotating electrode drum）在一電流密度為40A/dm2至80A/dm2的電流來進行電鍍； 其中： 在該電鍍的步驟進行時，該電解液中的總碳量維持在小於或等於0.25 g/L，且鈧（Sc）和釔（Y）的總濃度維持在小於或等於350mg/L；以及 使用粒徑（grit size）為800號至1500號之一拋光刷拋光該旋轉電極鼓的一表面。A method for manufacturing an electrolytic copper foil, the method includes: forming a copper layer; and forming a protective layer on the copper layer; wherein: the step of forming the copper layer includes: preparing an electrolytic solution, the electrolytic solution contains 50 g / L To 100 g / L copper ion, 50 g / L to 150 g / L sulfuric acid, 3 ppm to 12 ppm bis- (3-sulfopropyl) disulfide (SPS), and equal to or less than 50 ppm of chlorine; and electroplating through an electrode plate and a rotating electrode drum spaced apart from each other in the electrolyte at a current density of 40 A / dm2 to 80 A / dm2; wherein: in the When the electroplating step is performed, the total carbon content in the electrolyte is maintained at 0.25 g / L or less, and the total concentration of scandium (Sc) and yttrium (Y) is maintained at 350 mg / L or less; and the particle size is used; (Grit size) One of the 800 to 1500 polishing brushes polishes a surface of the rotary electrode drum. 如請求項12之電解銅箔的製造方法，其中製備該電解液的步驟包含： 在600°C至900°C的溫度範圍對一銅線進行熱處理30分鐘至60分鐘； 酸洗熱處理過的該銅線； 向該硫酸中置入酸洗過的該銅線。The method for manufacturing an electrolytic copper foil according to claim 12, wherein the step of preparing the electrolyte includes: heat-treating a copper wire at a temperature ranging from 600 ° C to 900 ° C for 30 minutes to 60 minutes; Copper wire; The pickled copper wire was placed in the sulfuric acid. 如請求項12之電解銅箔的製造方法，其中形成該銅層的步驟更包含在進行電鍍的步驟時將過氧化氫和空氣注入該電解液中。The method for manufacturing an electrolytic copper foil according to claim 12, wherein the step of forming the copper layer further includes injecting hydrogen peroxide and air into the electrolytic solution during the step of performing electroplating. 如請求項12之電解銅箔的製造方法，其中該電解液更包含至少一有機添加劑，該有機添加劑係選自羥乙基纖維素（hydroxyethyl cellulose．HEC）、有機硫化物、有機氮化物、乙二醇基聚合物和硫脲類化合物所組成的群組。The method of manufacturing the electrolytic copper foil according to claim 12, wherein the electrolyte further comprises at least one organic additive selected from the group consisting of hydroxyethyl cellulose (HEC), organic sulfide, organic nitride, and ethyl acetate. A group of glycol-based polymers and thioureas. 如請求項12之電解銅箔的製造方法，其中形成該保護層的步驟包含將該銅層浸泡在含有0.5g/L至1.5g/L的鉻的一防鏽溶液中。The method for manufacturing an electrolytic copper foil as claimed in claim 12, wherein the step of forming the protective layer includes immersing the copper layer in a rust-proof solution containing 0.5 g / L to 1.5 g / L of chromium.
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