KR101262721B1 - Electrolyte for manufacturing electrolytic copper foil of secondary battery and method for manufacturing electrolytic copper foil therewith - Google Patents

Electrolyte for manufacturing electrolytic copper foil of secondary battery and method for manufacturing electrolytic copper foil therewith Download PDF

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KR101262721B1
KR101262721B1 KR1020100055005A KR20100055005A KR101262721B1 KR 101262721 B1 KR101262721 B1 KR 101262721B1 KR 1020100055005 A KR1020100055005 A KR 1020100055005A KR 20100055005 A KR20100055005 A KR 20100055005A KR 101262721 B1 KR101262721 B1 KR 101262721B1
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copper foil
electrolytic copper
ppm
gelatin
electrolytic
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KR20110135219A (en
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황덕영
류종호
김상범
양창열
장영욱
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일진머티리얼즈 주식회사
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    • 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
    • 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
    • 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

본 발명은 전극 활물질과의 우수한 밀착성을 가질 수 있도록 저조도 및 고광택 특성을 나타내는 전해 동박을 제조하기에 적합한 전해액 및 이를 이용한 저조도 및 고광택 특성을 나타내는 전해 동박의 제조방법에 관한 것이다. 본 발명은 저조도 및 고광택 특성을 나타내는 전해 동박을 제조하기 위한 전해액 및 이를 이용한 전해 동박의 제조방법을 제공함으로써, 표면 거칠기(Rz)가 1.5 ㎛ 이하이며, 40 이상의 고광택 특성을 가진 전해 동박을 제조하고 이를 이차전지용 음극 집전체로서 활용하여 이차전지의 효율을 향상시킬 수 있다.The present invention relates to an electrolytic solution suitable for producing an electrolytic copper foil exhibiting low roughness and high glossiness so as to have excellent adhesion with an electrode active material, and a method for producing an electrolytic copper foil exhibiting low roughness and high glossiness using the same. The present invention provides an electrolytic solution for producing an electrolytic copper foil exhibiting low roughness and high gloss characteristics and a method for producing an electrolytic copper foil using the same, thereby producing an electrolytic copper foil having a surface roughness (R z ) of 1.5 µm or less and having a high gloss characteristic of 40 or more. And by using this as a negative electrode current collector for secondary batteries can improve the efficiency of the secondary battery.

Description

이차전지용 전해 동박을 제조하기 위한 전해액 및 이를 이용한 전해 동박의 제조방법{ELECTROLYTE FOR MANUFACTURING ELECTROLYTIC COPPER FOIL OF SECONDARY BATTERY AND METHOD FOR MANUFACTURING ELECTROLYTIC COPPER FOIL THEREWITH}ELECTROLYTE FOR MANUFACTURING ELECTROLYTIC COPPER FOIL OF SECONDARY BATTERY AND METHOD FOR MANUFACTURING ELECTROLYTIC COPPER FOIL THEREWITH}

본 발명은 이차전지용 전해 동박을 제조하기 위한 전해액 및 이를 이용한 전해 동박의 제조방법에 관한 것으로, 보다 상세하게는 전극 활물질과의 우수한 밀착성을 가질 수 있도록 저조도 및 고광택 특성을 나타내는 전해 동박을 제조하기 위한 전해액 및 이를 이용한 저조도 및 고광택 특성을 나타내는 전해 동박의 제조방법에 관한 것이다.
The present invention relates to an electrolytic solution for producing an electrolytic copper foil for secondary batteries and a method for producing an electrolytic copper foil using the same, and more particularly, to produce an electrolytic copper foil having low roughness and high gloss characteristics so as to have excellent adhesion with an electrode active material. Electrolytic solution and the manufacturing method of the electrolytic copper foil which show the low roughness and high gloss property using the same are provided.

일반적으로 전해 동박은 전기ㆍ전자 산업분야에서 사용되는 PCB(Printed Circuit Board: 인쇄회로기판)의 기초 재료로서 널리 사용되는 것으로써, 슬림형 노트북 컴퓨터, 개인휴대단말기(PDA), 전자북, MP3 플레이어, 차세대 휴대폰, 초박형 평판 디스플레이 등의 소형 제품을 중심으로 그 수요가 급속히 증대되고 있다. 또한 전해 동박의 물성을 개선하여 이차전지의 음극 집전체로서도 널리 사용되고 있다.In general, electrolytic copper foil is widely used as a basic material for printed circuit boards (PCBs) used in the electric and electronic industries, and is suitable for slim notebook computers, personal digital assistants (PDAs), electronic books, MP3 players, The demand for these products is rapidly increasing, especially for small products such as next-generation mobile phones and ultra-thin flat panel displays. In addition, by improving the physical properties of the electrolytic copper foil, it is widely used as a negative electrode current collector of a secondary battery.

이러한 전해 동박은, 황산-황산구리 수용액을 전해액으로 하고, 백금 원소 또는 그 산화물 원소로 피복한 티탄판으로 이루어지는 불용성 양극과 상기 양극에 대향하는 음극으로 티탄제 드럼을 사용하여, 상기 양극과 음극 사이에 직류 전류를 인가함으로써 티탄제 드럼 표면에 전착 구리를 석출시키고, 이때 티탄제 드럼이 일정속도로 회전하고 있어, 석출된 전착 구리를 드럼 표면으로부터 떼어내어 연속적으로 권취하는 방법에 의해 제조된다.Such an electrolytic copper foil uses an insoluble anode made of a titanium plate coated with a sulfuric acid-copper sulfate solution as an electrolytic solution and a platinum element or an oxide element thereof, and a titanium drum as a cathode facing the anode, between the anode and the cathode. By applying a direct current, electrodeposited copper is deposited on the surface of the titanium drum. At this time, the titanium drum is rotated at a constant speed, and the electrodeposited copper is removed from the drum surface and manufactured by a method of winding continuously.

상술한 제박공정에서 얻어진 전해 동박은 필요에 따라, 절연 기판과의 접착력을 향상시키기 위해서 거침 처리 공정(Nodule 처리공정이라고도 함), 구리 이온의 확산을 방지하는 확산방지처리, 외부로부터의 산화를 방지하기 위한 방청처리, 절연기판과의 접착력을 보완시키는 화학적 접착력 향상처리 등의 추가적인 표면처리 공정을 거칠 수 있다. 표면처리 공정을 거치면 로우 프로파일(low profile) 인쇄회로용 동박이 되고, 표면 처리 공정 중에서 방청처리만 하게 되면 이차전지용 동박이 된다.The electrolytic copper foil obtained at the above-mentioned manufacturing process is, if necessary, in order to improve adhesion to the insulating substrate, a roughening process (also referred to as a Nodule treatment process), a diffusion preventing treatment for preventing the diffusion of copper ions, and prevention of oxidation from the outside. It may be subjected to an additional surface treatment process such as anti-rust treatment, chemical adhesion enhancement treatment to complement the adhesion to the insulating substrate. Through the surface treatment process, it becomes a copper foil for a low profile printed circuit, and if only the rust prevention treatment is performed in the surface treatment process, it becomes a secondary battery copper foil.

전착된 동박은 인쇄회로용으로 사용되는 경우에는 표면 처리된 후 절연 기판과 접착된 형태(라미네이트)로 PCB 가공 업체에 공급된다. 이에 비해 이차전지용으로 사용할 경우에는 방청 처리만을 거쳐서 이차전지 생성 업체에 공급된다.Electrodeposited copper foil, when used for printed circuits, is surface-treated and then supplied to PCB processing companies in the form of laminates (laminates) bonded to insulating substrates. In contrast, when used for secondary batteries, it is supplied to secondary battery generators only after rust prevention treatment.

전해 동박을 이차전지용 음극 집전체로 사용하는 경우에는 동박의 양면에 전극 활물질을 피복하여 사용한다. 이 경우 전해 동박 양쪽 면의 조도가 다른 경우에는 전지 특성이 달라지게 되므로 전해 동박의 양쪽 면의 조도가 같거나 비슷한 수준을 유지할 필요가 있다.When using an electrolytic copper foil as a negative electrode electrical power collector for secondary batteries, it coats and uses an electrode active material on both surfaces of copper foil. In this case, when the roughness of both surfaces of the electrolytic copper foil is different, the battery characteristics are different. Therefore, the roughness of both surfaces of the electrolytic copper foil needs to be maintained at the same or similar level.

일반적으로 전해도금 방식에 의해 생성되는 동박에는 두 가지의 서로 다른 면이 있다. 음극드럼에 접해있는 광택이 있는 광택면(Shiny side, S면)과 환원 석출에 의해 결정립이 성장하는 방향의 전해액에 접해 있는, 광택이 없는 석출면(Matte side, M면)이 있다. 또한 석출면(M면)의 표면 거칠기는 광택면(S면)의 표면 거칠기에 의해 영향을 받게 되는데 광택면(S면)의 표면 거칠기가 낮을수록 석출면(M면)의 표면 거칠기가 낮아지는 경향이 있다. In general, there are two different aspects of copper foil produced by electroplating. There is a glossy polished surface (S side) in contact with the cathode drum and a matte side (M side) in contact with the electrolyte in the direction in which crystal grains grow by reduction precipitation. In addition, the surface roughness of the precipitation surface (M surface) is affected by the surface roughness of the glossy surface (S surface). The lower the surface roughness of the glossy surface (S surface), the lower the surface roughness of the precipitation surface (M surface). There is a tendency.

상기 구리 전해액으로 제조되는 전해 동박의 양쪽 면의 조도를 일정하게 유지하기 위해서는 석출면의 표면 거칠기(Rz)가 1.5 ㎛ 이하이고 광택도는 40 이상인 것이 바람직하며, 석출면의 표면 거칠기가(Rz)가 1.3 ㎛ 이하이고 광택도는 50 이상인 것이 보다 바람직하다.In order to keep the roughness of both surfaces of the electrolytic copper foil made of the said copper electrolyte solution, it is preferable that the surface roughness Rz of a precipitation surface is 1.5 micrometers or less, and glossiness is 40 or more, and the surface roughness of the precipitation surface (Rz) It is more preferable that it is 1.3 micrometers or less, and glossiness is 50 or more.

또 소형 리튬 이차전지의 음극 활물질로 탄소재료를 사용하는 경우 약 1.5배 정도의 체적 팽창이 일어나는 것에 비해, 중대형 이차전지의 음극 활물질로 실리콘을 사용하는 경우 약 4배 정도의 체적 팽창이 일어난다. 이와 같이 중대형 이차전지에서는 큰 체적변화로 인해 충방전 사이클시 음극 집전체인 동박으로부터 활물질이 박리, 탈락하여 전지 특성이 급격히 저하되는 문제점이 발생될 수 있으므로, 전극 활물질과의 밀착성을 향상시키기 위하여 동박의 표면 조도가 낮아야 한다. In addition, when carbon material is used as a negative electrode active material of a small lithium secondary battery, volume expansion of about 1.5 times occurs, whereas when silicon is used as a negative electrode active material of a medium and large secondary battery, volume expansion of about 4 times occurs. As described above, in the medium and large secondary batteries, the active material may peel off or drop off from the copper foil, which is the negative electrode current collector, during the charge and discharge cycle due to a large volume change, thereby causing a problem in which the battery characteristics are sharply degraded. The surface roughness of the surface should be low .

또한 유기계 바인더와의 밀착성을 향상시키기 위해서는 동박 표면의 광택도 관리가 필요하다. 통상의 PCB용 고조도 특성을 나타내는 동박을 음극 집전체로 사용시 활물질과의 밀착력이 불균일하고 충방전시 활물질과의 박리가 일어나서 충방전 사이클 특성이 저하될 수 있다.Moreover, in order to improve adhesiveness with an organic binder, the glossiness management of the copper foil surface is necessary. When using a copper foil exhibiting a high roughness characteristics for a conventional PCB as a negative electrode current collector, the adhesion with the active material is uneven and peeling with the active material may occur during charging and discharging, thereby degrading charge and discharge cycle characteristics.

하이브리드 자동차(Hybrid Electric Vehicle, HEV)용 중대형 리튬전지의 음극 집전체로는 일반적으로 동박이 사용된다. 중대형 리튬전지의 음극 집전체로 사용되는 동박은 압연가공에 의한 압연 동박이 주로 사용되나, 제조비용이 고가이고 광폭의 동박을 제조하기 어려운 문제가 있다. 또한, 압연 동박은 압연 가공시 윤활유를 사용해야 하기 때문에 윤활유의 오염에 의해 활물질과의 밀착성이 저하되어 전지의 충방전 사이클 특성이 저하될 수 있다. Copper foil is generally used as a negative electrode current collector of a medium-to-large lithium battery for a hybrid electric vehicle (HEV). The copper foil used as a negative electrode current collector of a medium-large lithium battery is mainly a rolled copper foil by rolling, but has a problem in that manufacturing costs are high and it is difficult to manufacture a wide copper foil. In addition, since the rolled copper foil must use lubricating oil during rolling, adhesion to the active material may be degraded due to contamination of the lubricating oil, thereby degrading charge and discharge cycle characteristics of the battery.

따라서, 리튬 이차전지의 충방전 사이클 특성을 향상시키기 위해서는 리튬 이차전지의 체적 변화 및 발열 현상을 견딜수 있는, 고온에서 고강도를 가지는 전해 동박 및 전극 활물질과의 밀착성이 우수한 저조도 및 고광택 특성을 나타내는 전해 동박이 요구되고 있는 실정이다.Therefore, in order to improve the charge / discharge cycle characteristics of the lithium secondary battery, an electrolytic copper foil having high strength at high temperature and an electrolytic copper foil exhibiting low roughness and high gloss characteristics excellent in adhesion with an electrode active material capable of withstanding the volume change and exothermic phenomenon of the lithium secondary battery. This situation is required.

본 발명자들은 상술한 종래기술의 문제점을 해결하고자 저조도 및 고광택 특성을 나타내는 전해 동박을 제조할 수 있는 기술에 대해 예의 연구를 거듭하였고, 그 결과 젤라틴과 염소이온을 특정 함량으로 포함하는 황산구리 전해액을 사용하여 전해 동박을 제조하는 경우 전해 동박의 석출면과 광택면의 표면 조도가 상당히 낮고 우수한 광택 특성을 나타내는 것을 알게 되어 본 발명을 완성하기에 이르렀다.
In order to solve the above-mentioned problems of the prior art, the inventors have intensively studied a technique capable of manufacturing an electrolytic copper foil having low light and high gloss characteristics, and as a result, using a copper sulfate electrolyte containing a specific content of gelatin and chlorine ions. In the case of manufacturing the electrolytic copper foil, the surface roughness of the precipitated surface and the glossy surface of the electrolytic copper foil was found to be considerably low and exhibited excellent gloss characteristics.

본 발명의 목적은 이차전지의 음극 집전체로 사용되기에 적합한, 석출면 및 광택면 모두가 저조도 및 고광택 특성을 나타내는 전해 동박을 제조하기 위한 전해액을 제공하는 데 있다.An object of the present invention is to provide an electrolytic solution for producing an electrolytic copper foil, both of which has a low roughness and high gloss, suitable for use as a negative electrode current collector of a secondary battery.

본 발명의 다른 목적은 이차전지의 음극 집전체로 사용되기에 적합한 전해 동박을 제조하는 방법을 제공하는 데 있다.
Another object of the present invention is to provide a method for producing an electrolytic copper foil suitable for use as a negative electrode current collector of a secondary battery.

상기 목적을 달성하기 위하여, 본 발명은 전기분해에 의해 전해 동박을 제조하기 위해 사용되는 황산구리를 포함하는 전해액으로서, 젤라틴과 염소이온이 3:1 중량비로 포함되는 이차전지용 전해 동박을 제조하기 위한 전해액을 제공한다.In order to achieve the above object, the present invention is an electrolyte solution containing copper sulfate used for producing an electrolytic copper foil by electrolysis, the electrolyte solution for producing an electrolytic copper foil for secondary batteries containing gelatin and chlorine ions in a 3: 1 weight ratio To provide.

보다 상세하게는 전기분해에 의해 전해 동박을 제조하기 위해 사용되는 황산구리를 포함하는 전해액으로서, 젤라틴 3∼30 ppm 및 염소이온 0초과∼1 ppm을 포함하거나, 젤라틴 10∼30 ppm 및 염소이온 1초과∼3 ppm을 포함하거나, 젤라틴 15∼30 ppm 및 염소이온 3초과∼5 ppm을 포함하거나, 젤라틴 25∼30 ppm 및 염소이온 5초과∼7 ppm을 포함하거나, 혹은 젤라틴 30 ppm 및 염소이온 7초과∼10 ppm을 포함하는, 이차전지용 전해 동박을 제조하기 위한 전해액을 제공한다.More specifically, an electrolytic solution containing copper sulfate used for producing an electrolytic copper foil by electrolysis, which contains 3 to 30 ppm of gelatin and 0 to 1 ppm of chlorine ions, or 10 to 30 ppm of gelatin and 1 or more chlorine ions. Contains ~ 3 ppm, contains 15-30 ppm gelatin and greater than 3 ppm chlorine ions, contains 25-30 ppm gelatin and greater than 5-7 ppm chlorine ions, or contains 30 ppm gelatin and greater than 7 chlorine ions The electrolyte solution for manufacturing the electrolytic copper foil for secondary batteries containing -10 ppm is provided.

또한 본 발명은 아래와 같은 단계로 이루어지는 이차전지용 전해 동박의 제조방법을 제공한다. In addition, the present invention provides a method for producing an electrolytic copper foil for secondary batteries comprising the following steps.

황산구리 용액에 젤라틴 및 염소이온을 첨가하여 전해액을 제조하는 단계 및 상기 전해액에 양극과 음극을 침지시킨 후 전기를 인가하여 음극에 전해 동박을 형성하는 단계를 포함하며,Preparing an electrolytic solution by adding gelatin and chlorine ions to the copper sulfate solution, and immersing the positive electrode and the negative electrode in the electrolyte and applying electricity to form an electrolytic copper foil on the negative electrode,

상기 전해액에는 젤라틴과 염소이온이 3:1 중량비로 포함되는 것이 바람직하다.It is preferable that the electrolyte contains gelatin and chlorine ions in a 3: 1 weight ratio.

보다 상세하게는 본 발명의 이차전지용 전해 동박의 제조방법에서 사용되는 전해액에는 황산구리 용액에 젤라틴이 3∼30 ppm 첨가되는 경우 염소이온은 0초과∼1 ppm 첨가되고, 상기 전해액에 젤라틴이 10∼30 ppm 첨가되는 경우 염소이온은 1초과∼3 ppm 첨가되고, 젤라틴이 15∼30 ppm 첨가되는 경우 염소이온은 3초과∼5 ppm 첨가되고, 젤라틴이 25∼30 ppm의 함량으로 첨가되는 경우 염소이온은 5초과∼7 ppm 첨가되고, 그리고 젤라틴이 30 ppm의 함량으로 첨가되는 경우 염소이온은 7초과∼10 ppm 첨가되는 것이 보다 바람직하다.More specifically, when 3 to 30 ppm of gelatin is added to the copper sulfate solution to the electrolyte solution used in the method for producing an electrolytic copper foil for secondary batteries of the present invention, chlorine ions are added in excess of 0 to 1 ppm, and gelatin is 10 to 30 in the electrolyte solution. When ppm is added, chlorine ions are added in excess of 1 to 3 ppm. When gelatin is added in 15 to 30 ppm, chlorine ions are added in excess of 3 to 5 ppm. When gelatin is added in a content of 25 to 30 ppm, chlorine ions are added. When more than 5 ppm to 7 ppm is added, and gelatin is added in an amount of 30 ppm, more preferably 7 to 10 ppm of chlorine ions is added.

본 발명에 따라 제조된 이차전지용 전해 동박은 석출면의 표면 거칠기(Rz)가 1.5 ㎛ 이하이고 광택도가 40 이상인 특성을 가지게 되며, 전해 동박의 석출면과 광택면은 표면 조도 및 광택도가 동일하거나 비슷하게 된다.Electrolytic copper foil for secondary batteries prepared according to the present invention has a surface roughness (R z ) of the surface of the precipitation surface is 1.5 ㎛ or less and has a glossiness of 40 or more, the surface and gloss surface of the electrodeposited surface of the electrolytic copper foil Become the same or similar.

상술한 바와 같이 본 발명에 따라 제조된 전해 동박은 전극 활물질과의 우수한 밀착성을 가질 수 있도록 저조도 및 고광택 특성을 나타내어 이차전지용 음극 집전체로 사용될 수 있다.
As described above, the electrolytic copper foil prepared according to the present invention may be used as a negative electrode current collector for secondary batteries by exhibiting low light intensity and high gloss characteristics so as to have excellent adhesion with an electrode active material.

본 발명은 전극 활물질과의 우수한 밀착성을 가질 수 있도록 저조도 및 고광택 특성을 나타내는 전해 동박을 제조하기 위한 전해액 및 이를 이용한 전해 동박의 제조방법을 제공함으로써, 표면 거칠기(Rz)가 1.5 ㎛ 이하이며, 40 이상의 고광택 특성을 가진 전해 동박을 제조하고 이를 이차전지용 음극 집전체로서 활용하여 이차전지의 효율을 향상시킬 수 있다.
The present invention provides an electrolytic solution for producing an electrolytic copper foil exhibiting low roughness and high gloss characteristics so as to have excellent adhesion with an electrode active material and a method for producing an electrolytic copper foil using the same, wherein the surface roughness R z is 1.5 μm or less, It is possible to improve the efficiency of the secondary battery by manufacturing an electrolytic copper foil having a high gloss property of 40 or more and using it as a negative electrode current collector for a secondary battery.

이하 본 발명의 이차전지용 전해 동박을 제조하기 위한 전해액 및 이를 이용한 전해 동박의 제조방법을 상세히 설명한다.
Hereinafter, an electrolytic solution for producing an electrolytic copper foil for secondary batteries of the present invention and a method for producing an electrolytic copper foil using the same will be described in detail.

본 발명은 전기분해에 의해 전해 동박을 제조하기 위해 사용되는 황산구리를 포함하는 전해액으로서, 젤라틴과 염소이온을 포함하는 전해액을 제공한다.The present invention provides an electrolyte solution containing copper sulfate, which is used for producing an electrolytic copper foil by electrolysis, and which contains gelatin and chlorine ions.

상기 젤라틴은 소의 뼈, 가죽, 돼지의 뼈, 가죽, 생선 비닐 등으로부터 추출되는 젤라틴을 분해하여 제조된 것으로서, 원료가 특별히 한정되지 않으며, 모든 종류의 단백질을 분해하여 얻어지는 젤라틴을 포함하며, 특정 분자량에 대해 한정되지 않는다.The gelatin is prepared by decomposing gelatin extracted from bovine bone, leather, pork bone, leather, fish vinyl, etc., and the raw material is not particularly limited, and includes gelatin obtained by decomposing all kinds of proteins, and has a specific molecular weight. It is not limited about.

본 발명의 전기분해에 의해 전해 동박을 제조하기 위한 전해액은 황산구리를 포함하는 전해액으로 젤라틴과 염소이온을 포함하여 제조되며, 젤라틴과 염소이온은 3:1 중량비로 포함되는 것이 바람직하다.Electrolytic solution for producing an electrolytic copper foil by the electrolysis of the present invention is an electrolyte containing copper sulfate is prepared containing gelatin and chlorine ions, gelatin and chlorine ions are preferably included in a 3: 1 weight ratio.

보다 상세하게는, 본 발명에 따른 전해액에 젤라틴이 3∼30 ppm 첨가되는 경우 염소이온은 0초과∼1 ppm 첨가되고, 상기 전해액에 젤라틴이 10∼30 ppm 첨가되는 경우 염소이온은 1초과∼3 ppm 첨가되고, 젤라틴이 15∼30 ppm 첨가되는 경우 염소이온은 3초과∼5 ppm 첨가되고, 젤라틴이 25∼30 ppm의 함량으로 첨가되는 경우 염소이온은 5초과∼7 ppm 첨가되고, 그리고 젤라틴이 30 ppm의 함량으로 첨가되는 경우 염소이온은 7초과∼10 ppm 첨가되는 것이 바람직하다.More specifically, when 3 to 30 ppm of gelatin is added to the electrolyte according to the present invention, chlorine ions are added to more than 0 to 1 ppm, and when 10 to 30 ppm of gelatin is added to the electrolyte, the chlorine to more than 1 to 3 ppm. When ppm is added and gelatin is added at 15 to 30 ppm, chlorine ions are added in excess of 3 to 5 ppm, when gelatin is added in an amount of 25 to 30 ppm, chlorine ions are added in excess of 5 to 7 ppm, and gelatin is added. When added in an amount of 30 ppm, chlorine ions are preferably added in excess of 7 to 10 ppm.

상술한 함량에 따라 젤라틴 및 염소이온이 첨가된 전해액을 사용하여 전기분해에 의해 전해 동박을 제조하는 경우, 전해 동박의 석출면은 낮은 표면 조도 및 높은 광택 특성을 나타낸다.When electrolytic copper foil is manufactured by electrolysis using the electrolytic solution to which gelatin and chlorine ion were added according to the above-mentioned content, the precipitation surface of electrolytic copper foil shows low surface roughness and high glossiness.

이하에서 본 발명의 전해액을 사용하여 전해 동박을 제조하는 방법에 대해 설명한다.Hereinafter, the method of manufacturing an electrolytic copper foil using the electrolyte solution of this invention is demonstrated.

우선, 황산구리 용액에 젤라틴 및 염소이온을 3:1 중량비로 첨가하여 전해액을 제조한다.First, an electrolytic solution is prepared by adding gelatin and chlorine ions in a 3: 1 weight ratio to the copper sulfate solution.

보다 바람직하게는 상기 전해액에는 황산구리 용액에 젤라틴이 3∼30 ppm 첨가되는 경우 염소이온은 0초과∼1 ppm 첨가되고, 상기 전해액에 젤라틴이 10∼30 ppm 첨가되는 경우 염소이온은 1초과∼3 ppm 첨가되고, 젤라틴이 15∼30 ppm 첨가되는 경우 염소이온은 3초과∼5 ppm 첨가되고, 젤라틴이 25∼30 ppm의 함량으로 첨가되는 경우 염소이온은 5초과∼7 ppm 첨가되고, 그리고 젤라틴이 30 ppm의 함량으로 첨가되는 경우 염소이온은 7초과∼10 ppm 첨가될 수 있다.More preferably, when 3 to 30 ppm of gelatin is added to the copper sulfate solution, more than 0 to 1 ppm of chlorine ion is added to the electrolyte, and 10 to 30 ppm of gelatin is added to the electrolyte solution. Chlorine ions are added in excess of 3 to 5 ppm when gelatin is added in an amount of 15 to 30 ppm, chlorine ions are added in an amount of 5 to 7 ppm when gelatin is added in an amount of 25 to 30 ppm, and gelatin is 30 When added in an amount of ppm, chlorine ions may be added in excess of 7 to 10 ppm.

다음으로 전해조 내에 양극과 음극을 배치시킨다. 본 발명의 일 실시형태에 있어서, 상기 전해조 내에는 반(半)원통형 양극과 회전하는 원통형 음극이 일정한 간격을 유지시켜 배치시킬 수 있다.Next, the positive electrode and the negative electrode are placed in the electrolytic cell. In one embodiment of the present invention, the semi-cylindrical positive electrode and the rotating cylindrical negative electrode can be arranged at a constant interval in the electrolytic cell.

본 발명에서 양극으로는 납 합금 또는 이리듐 산화물을 피복시킨 티타늄을 사용할 수 있다. 음극으로는 스테인레스강에 크롬 도금을 하여 사용할 수도 있고 티타늄에 백금을 피복하여 사용할 수도 있다. 티타늄에 백금을 피복하여 음극으로 사용하는 것이 음극의 수명에 있어서 바람직하다.In the present invention, as the anode, titanium coated with lead alloy or iridium oxide may be used. The cathode may be used by chromium plating on stainless steel or by coating platinum on titanium. It is preferable in the life of a negative electrode to coat titanium with platinum and to use it as a negative electrode.

다음으로, 전해조 내의 양극과 음극이 배치된 사이로 본 발명의 전해액을 연속적으로 공급한다. 이후 양극과 음극 간에 직류 전류를 인가하는 경우 음극에서는 전해액 중의 구리이온이 소정 두께의 금속으로 환원되어 석출됨으로써 전해 동박이 형성된다. 이후 음극 표면으로부터 상기 전해 동박을 박리시키면서 연속적으로 권취하는 방법에 의해 전해 동박을 수득할 수 있다.Next, the electrolyte solution of the present invention is continuously supplied between the anode and the cathode in the electrolytic cell. Subsequently, when a direct current is applied between the positive electrode and the negative electrode, copper ions in the electrolyte are reduced and precipitated by a metal having a predetermined thickness, thereby forming an electrolytic copper foil. Then, an electrolytic copper foil can be obtained by the method of winding up continuously, peeling the said electrolytic copper foil from the negative electrode surface.

본 발명의 전해 동박의 제조방법에 따라 제조된 전해 동박은 석출면의 표면 거칠기(Rz)가 1.5 ㎛ 이하이며, 40 이상의 고광택 특성을 나타내며, 보다 바람직하게는 표면 거칠기(Rz)가 1.3 ㎛ 이하이며, 50 이상의 고광택 특성을 나타낸다. 따라서, 본 발명에 따른 전해액을 사용하여 전기 분해에 의해 전해 동박을 제조하는 경우 전해 동박의 석출면(M면)과 광택면(S면) 모두 동일하게 낮은 표면 조도 및 높은 광택 특성을 나타낸다.The electrolytic copper foil prepared according to the method for producing an electrolytic copper foil of the present invention has a surface roughness (R z ) of the precipitated surface of 1.5 μm or less, exhibits high glossiness of 40 or more, and more preferably, the surface roughness (R z ) of 1.3 μm. It is below and shows 50 or more high gloss characteristics. Therefore, when the electrolytic copper foil is produced by electrolysis using the electrolytic solution according to the present invention, both the precipitated surface (M surface) and the glossy surface (S surface) of the electrolytic copper foil exhibit the same low surface roughness and high gloss characteristics.

이와 같이 제조된 전해 동박에 대해 필요에 따라, 보관, 운송 과정에서 산화되는 것을 방지하기 위한 방청 처리를 더 실시할 수 있다.
As needed, the rust-preventing treatment for preventing the oxidation of the electrolytic copper foil thus produced, which is oxidized in the storage and transportation process can be further performed.

이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 설명한다. 하지만 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범주 및 기술사상 범위 내에서 다양한 변경 및 수정이 가능함은 당업자에게 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허 청구 범위에 속하는 것도 당연한 것이다.
Hereinafter, a preferred embodiment will be described in order to facilitate understanding of the present invention. 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 and scope of the invention as defined by the appended claims.

[실시예][Example]

전기분해법에 의한 전해 동박을 제조하기 위해 20 L/min으로 순환 가능한 3L 용량의 전해조 시스템을 이용하였고 전해액의 온도는 50℃로 일정하게 유지하였다. 양극은 두께가 5mm이고, 크기가 10ⅹ10 cm2의 DSE(Dimentionally Stable Electrode) 극판을 사용하였으며, 음극은 양극과 동일한 크기 및 두께를 가진 티타늄 극판을 사용하였다. 상기 전해액은 Cu2 + 농도를 87.5 g/L, SO4 2 - 농도가 125 g/L인 조성의 용액으로 제조하였고, 젤라틴(C&A Biotech)은 0초과 50ppm의 함량으로 첨가하였고, 염소이온은 0초과 10ppm의 함량으로 첨가하였다. 전극간 거리는 10mm로 일정하게 유지하였으며, Cu2+ 이온의 이동을 원활하게 하기 위하여 전류밀도는 60 A/dm2를 인가하여 전해도금을 실시하여, 18㎛ 두께의 전해 동박을 제조하였다. 전해액에 포함된 젤라틴과 염소이온의 함량에 따른 전해 동박 석출면의 표면 거칠기(Rz) 및 광택도를 측정하여 각각 표 1 및 표 2에 나타내었다.
In order to manufacture the electrolytic copper foil by electrolysis, a 3L electrolytic cell system circulating at 20 L / min was used, and the temperature of the electrolyte solution was kept constant at 50 ° C. The anode was a 5mm thick, 10 × 10 cm 2 DSE (Dimentionally Stable Electrode) electrode plate, the cathode was used as a titanium electrode plate having the same size and thickness as the anode. The electrolyte solution was prepared as a solution having a composition of Cu 2 + concentration of 87.5 g / L, SO 4 2 - concentration of 125 g / L, gelatin (C & A Biotech) was added in a content of more than 0 and 50 ppm, chlorine ion is 0 It was added at a content of more than 10 ppm. The distance between the electrodes was constantly maintained at 10 mm, and in order to facilitate the movement of Cu 2+ ions, electrolytic plating was performed by applying a current density of 60 A / dm 2 to prepare an electrolytic copper foil having a thickness of 18 μm. The surface roughness (R z ) and glossiness of the electrodeposited copper foil precipitated surface according to the gelatin and chlorine ions contained in the electrolyte were measured and shown in Table 1 and Table 2, respectively.

물성측정방법How to measure property

실시예에서 얻어진 전해 동박의 석출면의 표면 거칠기(Rz)를 JISB 0601-1994 규격에 따라 측정하였다. 상기 측정방법에 따라 얻어진 전해 동박의 석출면의 표면 거칠기(Rz)를 하기 표 1에 나타내었다. 표면 거칠기(Rz) 값이 낮을수록 표면 조도가 낮음을 의미한다.The surface roughness (R z ) of the precipitation surface of the electrolytic copper foil obtained in the examples was measured according to the JISB 0601-1994 standard. The surface roughness (R z ) of the precipitation surface of the electrolytic copper foil obtained according to the above measuring method is shown in Table 1 below. Lower surface roughness (R z ) value means lower surface roughness.

실시예에서 얻어진 전해 동박의 석출면의 광택도를 측정하기 위해Nippon Denshoku(Model : VG-2000) 장비를 이용하여 JIS Z 8741 규격에 따라 측정하였다. 상기 측정방법에 따라 얻어진 전해 동박의 석출면의 광택도를 표 2에 나타내었다. 광택도 값이 커질수록 광택도가 좋음을 의미한다.
In order to measure the glossiness of the precipitation surface of the electrolytic copper foil obtained in the example, it was measured according to JIS Z 8741 standard using a Nippon Denshoku (Model: VG-2000) equipment. The glossiness of the precipitation surface of the electrolytic copper foil obtained by the said measuring method is shown in Table 2. The higher the gloss value, the better the gloss.

Figure 112010037418581-pat00001
Figure 112010037418581-pat00001

Figure 112010037418581-pat00002
Figure 112010037418581-pat00002

상기 표 1 및 표 2를 참조하면, 본 발명에 따른 황산구리를 포함한 전해액에 젤라틴과 염소이온이 본 발명에서 한정한 특정함량으로 포함되는 경우, 상기 전해액을 사용하여 전기 분해법에 의해 제조된 전해 동박의 석출면은 표면 거칠기(Rz)가 1.3 ㎛ 이하로 낮게 나타나며, 광택도가 50 이상을 나타냄을 알 수 있다. Referring to Table 1 and Table 2, when gelatin and chlorine ions are contained in the electrolyte solution containing copper sulfate according to the present invention in a specific content defined in the present invention, the electrolytic copper foil prepared by the electrolytic method using the electrolyte solution As for the precipitated surface, the surface roughness (R z ) is lower than 1.3 μm, and it can be seen that the glossiness is 50 or more.

이와 같이 본 발명에 따라 전기 분해법에 의해 제조된 전해 동박의 석출면의 표면 거칠기(Rz)가 1.3 ㎛ 이하로 낮게 나타나는 경우 전해 동박의 광택면의 표면 거칠기 또한 석출면과 동일하게 낮게 나타난다.As such, when the surface roughness R z of the precipitated surface of the electrolytic copper foil manufactured by the electrolytic method according to the present invention is lower than 1.3 μm, the surface roughness of the glossy surface of the electrolytic copper foil also appears to be the same as the precipitated surface.

Claims (15)

삭제delete 삭제delete 삭제delete 삭제delete 삭제delete 삭제delete 표면 거칠기(Rz)가 1.3 ㎛ 이하이고, 광택도가 50 이상의 이차전지용 전해 동박의 제조방법으로서,
황산구리 용액에 젤라틴 및 염소 이온을 첨가하여 전해액을 제조하는 단계 및 상기 전해액에 양극과 음극을 침지시킨 후 전기를 인가하여 음극에 전해 동박을 형성하는 단계를 포함하며,
상기 전해액에 젤라틴과 염소 이온이 3:1 중량비로 첨가되고,
상기 젤라틴과 염소 이온 농도가, 젤라틴 농도 3∼30 ppm, 염소 이온 농도 0초과∼1 ppm; 젤라틴 농도 10∼30 ppm, 염소 이온 농도 1초과∼3 ppm; 젤라틴 농도 15∼30 ppm, 염소 이온 농도 3초과∼5 ppm; 젤라틴 농도 25∼30 ppm, 염소 이온 농도 5초과∼7 ppm; 및 젤라틴 농도 30 ppm, 염소 이온 농도 7초과∼10 ppm로 이루어지는 군으로부터 선택되는 하나의 조합으로 포함되는 것을 특징으로 하는, 이차전지용 전해 동박의 제조방법.
As a manufacturing method of the electrolytic copper foil for secondary batteries whose surface roughness Rz is 1.3 micrometers or less, and glossiness is 50 or more,
Preparing an electrolytic solution by adding gelatin and chlorine ions to the copper sulfate solution, and immersing the positive electrode and the negative electrode in the electrolyte and applying electricity to form an electrolytic copper foil on the negative electrode,
Gelatin and chlorine ions are added to the electrolyte in a 3: 1 weight ratio,
The gelatin and chlorine ion concentrations range from 3 to 30 ppm of gelatin concentration and from 0 to 1 ppm of chlorine ion concentration; Gelatin concentration of 10 to 30 ppm, chlorine ion concentration of greater than 1 to 3 ppm; Gelatin concentration of 15 to 30 ppm, chlorine ion concentration of greater than 3 to 5 ppm; Gelatin concentration 25-30 ppm, chlorine ion concentration 5 to 7 ppm; And a combination selected from the group consisting of gelatin concentration of 30 ppm and chlorine ion concentration of greater than 7 to 10 ppm.
삭제delete 삭제delete 삭제delete 삭제delete 삭제delete 삭제delete 삭제delete 청구항 7에 있어서,
석출면과 광택면의 표면 거칠기 및 광택도가 동일한 것을 특징으로 하는 이차전지용 전해 동박의 제조방법.
The method of claim 7,
The surface roughness and glossiness of a precipitation surface and a glossy surface are the same, The manufacturing method of the electrolytic copper foil for secondary batteries characterized by the above-mentioned.
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JP2007217791A (en) 2005-03-31 2007-08-30 Mitsui Mining & Smelting Co Ltd Electrolytic copper foil, surface-treated electrolytic copper foil obtained by using the electrolytic copper foil, copper-clad laminate using the surface-treated electrolytic copper foil, and printed circuit board
JP2007247007A (en) 2006-03-16 2007-09-27 Mitsui Mining & Smelting Co Ltd Copper electrolyte, method for manufacturing additive used for copper electrolyte, and electrodeposition copper film obtained by using the copper electrolyte

Patent Citations (3)

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JP2006152420A (en) 2004-12-01 2006-06-15 Mitsui Mining & Smelting Co Ltd Electrolytic copper foil and method for producing the same
JP2007217791A (en) 2005-03-31 2007-08-30 Mitsui Mining & Smelting Co Ltd Electrolytic copper foil, surface-treated electrolytic copper foil obtained by using the electrolytic copper foil, copper-clad laminate using the surface-treated electrolytic copper foil, and printed circuit board
JP2007247007A (en) 2006-03-16 2007-09-27 Mitsui Mining & Smelting Co Ltd Copper electrolyte, method for manufacturing additive used for copper electrolyte, and electrodeposition copper film obtained by using the copper electrolyte

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