US20040104117A1 - Electrolyte solution for manufacturing electrolytic copper foil and electrolytic copper foil manufacturing method using the same - Google Patents

Electrolyte solution for manufacturing electrolytic copper foil and electrolytic copper foil manufacturing method using the same Download PDF

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Publication number
US20040104117A1
US20040104117A1 US10/713,795 US71379503A US2004104117A1 US 20040104117 A1 US20040104117 A1 US 20040104117A1 US 71379503 A US71379503 A US 71379503A US 2004104117 A1 US2004104117 A1 US 2004104117A1
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US
United States
Prior art keywords
copper foil
electrolyte solution
electrolytic copper
thioalkan
compound
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Abandoned
Application number
US10/713,795
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English (en)
Inventor
Jeom-Sik Yang
Seung-Lin Lim
Sang-Beom Kim
Ki-Jung Kim
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Iljin Copper Foil Co Ltd
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Iljin Copper Foil Co Ltd
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Application filed by Iljin Copper Foil Co Ltd filed Critical Iljin Copper Foil Co Ltd
Assigned to ILJIN COPPER FOIL CO., LTD. reassignment ILJIN COPPER FOIL CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KIM, KI-JUNG, KIM, SANG-BEOM, LIM, SEUNG-LIN, YANG, JEOM-SIK
Publication of US20040104117A1 publication Critical patent/US20040104117A1/en
Abandoned legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils
    • C25D7/0635—In radial cells
    • 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

Definitions

  • the present invention generally relates to an electrolyte solution used to manufacture an electrolytic copper foil for a printed circuit and an electrolytic copper foil for an electrode collector of a secondary battery, the electrolytic copper foil using the same, and an electrolytic copper foil manufacturing method thereof.
  • a printed circuit board using the electrolytic copper foil is widely used as a precise control circuit of various electric, electronic communication apparatuses such as radios, TVs, computers, telephone exchanges, wireless transceivers, etc. Recently, as a degree of integration of the printed circuit board increases, circuits of the board get minute and multilayered. Particularly, the electrolytic copper foil is highly demanded in terms of COF (Chip On Flex) and TAB (Tape Automatic Bonding) aspects, and is broadly used as an electrode collector of a secondary battery by improving its physical properties.
  • the electrolytic copper foil is created by electrolytic methods, and is manufactured from a cylinder-shaped cathode (also, called a drum) consisting of titanium, an anode consisting of a lead alloy keeping certain intervals or titanium covered by an iridium oxide, and an electrolytic cell including an electrolyte solution and current power.
  • the electrolyte solution is composed of sulfuric acid and/or a copper sulfate.
  • the copper foil obtained from the thin film process can pass through additional surface treatment processes including a roughness treatment process (also, called a nodule treatment process), a nonproliferation process to prevent the copper ion from being proliferated, an anticorrosive process to prevent oxidation from outside, a chemical adhesive force improving process to complement an adhesive force with the insulating substrate, and so on.
  • a roughness treatment process also, called a nodule treatment process
  • an anticorrosive process to prevent oxidation from outside
  • a chemical adhesive force improving process to complement an adhesive force with the insulating substrate, and so on.
  • the copper foil is supplied to a PCB (Printed Circuit Board) process manufacturer while being adhered (laminated) to the insulating substrate after the surface treatment process.
  • the copper foil is supplied to a secondary battery manufacturer via the anticorrosive process only.
  • the surface of the copper foil contacted with the insulating substrate should have a small roughness.
  • the copper foil gets stress by thermal expansion or heat-shrink and moreover, the copper foil is laminated in multilayer way, it may have scratches due to friction with a neighboring copper foil. More seriously, the copper foil can be exfoliated from the insulating substrate or have circuit damage, or a PCB may get bent or distorted. To protect the copper foil from these problems, it is necessary to have a proper elongation without suddenly deteriorating mechanical intensity at high temperature.
  • the electrolytic copper foil When the electrolytic copper foil is used as the collector for the secondary battery, electrode materials should cover both sides of the copper foil. In this case, if both sides of the electrolytic copper foil have a different roughness, battery characteristics differ from each side. Therefore, it is required to have the same or a similar roughness on both sides of the electrolytic copper foil. Furthermore, to reduce weight and a manufacturing cost of the battery and increase energy density of the battery, the electrolytic copper foil should be manufactured in thin type. Even though the copper foil is thin, it is necessary to have sufficient mechanical intensity and an elongation at high temperature, without being bent in a future treatment process.
  • the prior art has suggested a method of making an electrolytic copper foil by adding various organic additives to an electrolyte solution.
  • the U.S. Pat. No. 5,431,803 has been suggested to lower a surface roughness, providing a method of manufacturing an electrolytic copper foil that maintains concentration of a chlorine ion less than 1 mg in a 1-liter electrolyte solution.
  • 5,431,803 has 61 kgf/mm 2 to 84 kgf/m 2 of mechanical intensity at room temperature as well as 17 kgf/mm 2 to 25 kgf/mm 2 at 180° C., and has about 6 ⁇ m of the maximum value of the surface roughness: Rmax for a surface treatment.
  • Rmax the maximum value of the surface roughness
  • the present invention provides the electrolyte solution, the electrolytic copper foil produced by using the electrolyte solution, and an electrolytic copper foil manufacturing method thereof.
  • an electrolyte solution containing at least selected one of sulfuric acid and copper sulfate used to manufacture an electrolytic copper foil by electrolysis the electrolyte solution for manufacturing the electrolytic copper foil, based on the 1-liter electrolyte solution, comprising: 0.5 to 40 mg of at least one sulfur compound selected from a disulfur compound, dialkylamino- T-oxomethyl- thioalkan sulfonic acid, and thioalkan sulfonic acid salt; 1 to 1000 mg of at least more than one kind of an organic compound selected from a group consisting of a poly aklylene glycol-type surfactant and low molecular gelatin; and 0.1 to 80 mg of chlorine ion added.
  • a solution comprising i) sulfuric acid and copper salt rather than copper sulfate, or ii) copper sulfate and acid rather than sulfuric acid may be also used as the electrolyte.
  • the organic compound comprising low molecular gelatin without polyalkylene gulycol type surfactant may be also used as the organic compound.
  • a process of manufacturing an electrolytic copper foil for a printed circuit is divided into a thin film process and a surface treatment process.
  • the thin film process is generally performed by using an electroforming cell.
  • an electrolytic cell Within an electrolytic cell, a semi-cylinder type anode and a cylinder-type rotating cathode are located at certain intervals, and the electrolyte solution is consecutively supplied between the anode and the cathode.
  • a copper ion of the electrolyte solution is restored to metal having predetermined thickness from the cathode.
  • a copper foil (undisposed) that does not pass through a future treatment process is exfoliated from the surface of the cathode.
  • a lead alloy is widely used for the anode, but recently, intervals are changed by corrosion of a lead oxide. Therefore, titanium covering an iridium oxide is more used.
  • the cathode is used by plating iron with chromium, however recently, stainless materials are covered with titanium to lengthen the span of life.
  • an additional treatment process of passing the undisposed copper foil through a processor can be performed.
  • This treatment process includes a roughness treatment process to improve an adhesive force when laminated on an insulating substrate, a nonproliferation process to prevent a copper ion from being proliferated, and an anticorrosive process to prevent oxidation during storage, transportation or a lamination forming process of the copper foil and the insulating substrate.
  • a roughness treatment process to improve an adhesive force when laminated on an insulating substrate
  • a nonproliferation process to prevent a copper ion from being proliferated
  • an anticorrosive process to prevent oxidation during storage, transportation or a lamination forming process of the copper foil and the insulating substrate.
  • the electrolyte solution supplied between the anode and the cathode is a copper sulfate solution, and its blending based on 1 liter is as follows:
  • Copper concentration is between 50 g and 110 g, and desirably, between 60 g and 100 g.
  • Sulfuric acid concentration is between 80 g and 200 g, and desirably, between 90 g and 120 g.
  • Temperature of the electrolyte solution is between 40° C. and 80° C.
  • Current density is between 400A/cm 2 and 10000A/dm 2 , and desirably, between 50A/dm 2 and 85A/dm 2 . If the copper concentration is less than 50 g, the surface of an electrodeposited copper foil is rough and powder is formed, lowering productivity. However, if more than 110 g, the electrolyte solution is crystallized, deteriorating working efficiency.
  • the sulfuric acid concentration is less than 80 g, an electrolytic voltage rises, resulting in an increase of production cost. Also, temperature of the electrolyte solution rises, causing deterioration of mechanical intensity of the copper foil. If the sulfuric acid concentration is more than 200 g, the electrolyte solution is highly apt to be corrosive even though the electrolytic voltage lowers, thereby quickly corroding an electrode electrolyzing the copper foil.
  • the electrolyte solution contains a sulfur compound having 0.5 to 40 mg of concentration and at least more than one kind of an organic compound selected from a group consisting of a poly alkylene glycol-type surfactant having 1 to 1000 mg of concentration and low molecular gelatin as additives.
  • a chlorine ion having a range of 0.1 mg to 80 mg is added.
  • a nitrogen compound for example, IM(2-imidazolidiniethionie) is used within a range of 0.1 mg to 8 mg.
  • IM(2-imidazolidiniethionie) is used within a range of 0.1 mg to 8 mg.
  • the poly alkylene glycol-type surfactant it is available to use poly ethylene-type, poly propylene-type, and poly butylenes-type surfactants.
  • poly ethylene glycol can be representative of the poly ethylene-type surfactant.
  • a disulfur compound and dialkylamino- T-oxomethyl- thioalkan sulfonic acid or thioalkan sulfonic acid salt are included in the sulfur compound.
  • the disulfur compound includes SPS (Bis-(3-sulfopropyl)-disulfide, disodium salt)), and dialkylamino- T-oxomethyl- thioalkan sulfonic acid or salt thereof can contain dithiocarbamic acid or salt thereof, and DPS (N,N-Dimethyldithiocarbamic acid (3-sulfopropyl) ester, sodium salt) is representative.
  • a formula of the dialkylamino- T-oxomethyl- thioalkan sulfonic acid or the salt thereof is shown in a chemical formula 1, and a formula of the DPS as a representative example is shown in a chemical formula 2, then a formula of the SPS is shown in a chemical formula 3.
  • R in the chemical formula 1 means an alkyl group (carbon atom 1 ⁇ 6)
  • n is 2 ⁇ 3 (ethane, propane)
  • X means hydrogen atom or alkali metal atom.
  • the roles of the sulfur compound and the surfactant are very important, since these compounds give direct influence on a surface roughness and tensile strength.
  • the sulfur compound Compared to a general electrolytic copper foil added with glue or gelatin, the sulfur compound generally has a small size of grains and functions as a grain refiner or a brightener.
  • the added surfactant functions as a carrier or an electrodeposition leveler lowering a surface roughness of a mat surface of the electrolytic copper foil, influencing electroposition.
  • the surfactant is absorbed into a protruded part of an electrode surface as carrying the sulfur compound, which is a brightener, to a cathode surface, and suppresses growth of the protruded part, thereby interrupting the growth firstly.
  • the sulfur compound which is the grain refiner, firstly functions in a minute valley part of an electroposition surface, and enables a copper ion to be restored and grow up in this part first of all, thereby controlling a roughness of the electrodeposition surface.
  • the thiourea derivative, the nitrogen compound used in the present invention suppresses crystal growth of copper at room temperature or high temperature by eutectoid-processing nitrogen on an electrodeposition layer, and also restrains strength deterioration.
  • the nitrogen compound, the thiourea derivative when added, it is possible to prevent the strength deterioration, which occurs otherwise. So, a defective proportion caused when dealing with the electrolytic copper foil or manufacturing the printed circuit can be reduced.
  • the strength can be changed by controlling an amount of the additives, thereby adjusting physical properties of the electrolytic copper foil.
  • the above undisposed copper foil can pass through additional surface treatment processes including a roughness treatment process (also, called a nodule treatment process), a nonproliferation process to prevent a copper ion from being proliferated, and an anticorrosive process to prevent oxidation from outside. If passing through the surface treatment process, the copper foil is made for a low profile printed circuit, however, if passing through the anticorrosive process only, the copper foil is for a secondary battery.
  • a roughness treatment process also, called a nodule treatment process
  • a nonproliferation process to prevent a copper ion from being proliferated
  • an anticorrosive process to prevent oxidation from outside.
  • the roughness treatment process consists of two steps or three steps.
  • a core of minute powder is made, and the powder is coupled with the copper foil in a second step because the powder does not have an adhesive force with the copper foil.
  • a minute protrusion is given to the coupled powder again.
  • the first step is as follows. Based on a 1-liter electrolyte solution, copper concentration is between 10 g and 40 g, and desirably, between 15 g and 25 g. Sulfuric acid concentration is between 40 g and 150 g, and desirably between 60 g and 100 g, and temperature of the electrolyte solution is between 20° C. and 40° C.
  • Current density is between 20 A/dm 2 and 100 A/dm 2 , and desirably, between 40 A/dm 2 and 80 A/dm 2 .
  • the second step is as follows. Copper concentration is between 50 g and 110 g, and desirably, between 55 g and 100 g. Sulfuric acid concentration is between 80 g and 200 g, and desirably, between 90 g and 120 g. Temperature of the electrolyte solution is between 40° C. and 80° C. Current density is between 20 A/dm 2 and 100 A/dm 2 , and desirably, between 40 A/dm 2 and 80 A/dm 2 .
  • the nonproliferation process is as follows.
  • a barrier layer is formed with various single metal such as zinc, nickel, iron, cobalt, molybdenum, tungsten, tin, indium, and chrome, or with 2 or 3 kinds of alloys.
  • the anticorrosive process performs chromate passivation with chromic acid, sodium dichromate, potassium dichromate, chromic anhydride, etc.
  • a process for increasing chemical cohesion is executed.
  • a chemical adhesive force improving process can be carried out to complement an adhesive force with the insulating substrate.
  • adhesion accelerators such as a silane coupling agent (RSiX 3 ), silicon peroxygen (R 4 ⁇ n Si(OOR′) n ), a chromium-based adhesion accelerator ((RCO 2 H 3 OHCrOHCrHOH 2 ) 2 OH), an organic titanium based adhesion accelerator ((C 4 H 9 CHC 2 H 5 CH 2 O) 4 Ti), an organic phosphate based adhesion accelerator (RO 2 P(OH) 2 ), and others.
  • silane coupling agent RSiX 3
  • silicon peroxygen R 4 ⁇ n Si(OOR′) n
  • a chromium-based adhesion accelerator (RCO 2 H 3 OHCrOHCrHOH 2 ) 2 OH)
  • an organic titanium based adhesion accelerator (C 4 H 9 CHC 2 H 5 CH 2 O) 4 Ti)
  • a symbol ‘g/L’ means a content of a corresponding material based on a 1-liter electrolyte solution.
  • the electrolyte solution having blending like described in Table 1 is prepared. Copper concentration of the electrolyte solution is 80 g/L, sulfuric acid concentration is 90 g/L, and temperature of the electrolyte solution is 45° C. Additives like described in Table 1 have been added. Current density was electrodeposited in 60 A/dm 2 , and chlorine ion was maintained in 25 mg/L.
  • SPS Bis-(3-sulfopropyl)-disulfide, disodium salt
  • PEG Poly Ethylene Glycol
  • SPS Bis-(3-sulfopropyl)-disulfide, disodium salt
  • PEG Poly Ethylene Glycol
  • an Rz value tended to exceed 2.0 ⁇ m by an increase of a surface roughness of a rough surface in a range of exceeding 40 mg/L.
  • the surface roughness did not lower, rather the roughness increased as lowering an elongation.
  • the poly ethylene glycol-type surfactant it was possible to confirm a function of lowering the surface roughness of the rough surface within a range of 1 mg/L to 1000 mg/L. More desirably, a desirable surface roughness could be obtained within a range of 1 mg/L to 300 mg/L. However, in this case, it was required to control using current density in higher or lower way according to its amount.
  • a surface treatment process was carried out for the undisposed copper foil in accordance with the embodiments 1 to 7.
  • 110 g/L of sodium cyanide, 60 g/L of sodium hydroxide, 90 g/L of copper cyanide, and 5.3 g/L of zinc cyanide have been electrodeposited with pH 11.0 to 11.5 at 50° C., having 5 A/dm 2 of current density for 10 seconds.
  • 10 g/L of sodium dichromate has been measured with pH 4.5, having 0.5 A/dm 2 of current density for 2 seconds.
  • composition of the electrolyte solution and the chlorine ion concentration are the same as the above embodiments.
  • 2 mg/L of low molecular gelatin less than 6000 molecular weight has been added as an additive.
  • 1 mg/L of TU (thiourea) has been added with 2 mg/L of low molecular gelatin less than 6000 molecular weight.
  • 50 mg/L and 30 mg/L of SPS and PEG, respectively have been added.
  • Table 2 shows the results of comparing physical properties of the copper foil tentatively manufactured through the embodiments and the compared examples under the condition suggested in Table 1.
  • a roughness (Rz) of a rough surface is controlled less than 2.0 by the sulfur compound.
  • Rz a roughness of a drum surface and change strength
  • DPS N-Dimethyldithiocarbamic acid (3-sulfopropyl) ester, sodium salt
  • SPS Bis-(3-sulfopropyl)-disulfide, disodium salt
  • the electrolytic copper foil manufactured in the embodiments in accordance with the present invention has a surface roughness Rz value of a rough surface within a range of 2.0 ⁇ m in a thin film state. It is also confirmed that tensile strength at room temperature is not rapidly changed even at high temperature (180° C.) as well.
  • An electrolytic copper foil in accordance with the present invention has a roughness Rz value of a rough surface (mat surface) with a range of less than 2.0 ⁇ m, if undisposed. However, if the copper foil passes through a surface treatment process, it has a roughness Rz value of a rough surface (mat surface) within a range of 1.0 ⁇ 3.5 ⁇ m. Therefore, the electrolytic copper foil in accordance with the present invention has a relatively lower roughness on the rough surface, and both sides of the electrolytic copper foil have a similar roughness.
  • An electrolytic copper foil manufactured in prior art has a problem of rapidly causing strength deterioration at high temperature (180° C.), though good strength is maintained at room temperature.
  • the electrolytic copper foil in accordance with the present invention does not show any sudden strength change even at high temperature. Accordingly, the electrolytic copper foil in accordance with the present invention is appropriate for a minute and highly integrated PCB circuit.
  • the electrolytic copper foil in accordance with the present invention prevents tensile strength from suddenly deteriorating owing to a temperature rise, having excellent elongation characteristics at room temperature and high temperature. Thus, it would not get bent or distorted in a future treatment process nor generate a short circuit.
  • the electrolytic copper foil in accordance with the present invention is proper to be used as the collector for the secondary battery or a printed circuit board.

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US10/713,795 2002-11-14 2003-11-13 Electrolyte solution for manufacturing electrolytic copper foil and electrolytic copper foil manufacturing method using the same Abandoned US20040104117A1 (en)

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US (1) US20040104117A1 (ko)
JP (1) JP2004162172A (ko)
KR (1) KR100389061B1 (ko)
CN (1) CN1263899C (ko)
CA (1) CA2448892A1 (ko)
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US20070235343A1 (en) * 2006-04-05 2007-10-11 James Watkowski Process for electrolytically plating copper
WO2008041706A1 (fr) 2006-10-03 2008-04-10 Mitsui Mining & Smelting Co., Ltd. procÉdÉ de prÉparation d'une solution de cuivre Électrolytique acidifiÉe au moyen d'acide sulfurique, solution de cuivre Électrolytique acidifiÉe au moyen d'acide sulfurique prÉparÉe par le procÉdÉ de prÉparation et film de cuivre Éle
US20080142249A1 (en) * 2006-12-13 2008-06-19 International Business Machines Corporation Selective surface roughness for high speed signaling
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US20100084275A1 (en) * 2007-03-15 2010-04-08 Mikio Hanafusa Copper electrolytic solution and two-layer flexible substrate obtained using the same
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US9457541B2 (en) 2010-07-15 2016-10-04 Ls Mtron Ltd. Copper foil for current collector of lithium secondary battery with improved wrinkle characteristics
US9890463B2 (en) 2011-07-29 2018-02-13 Furukawa Electric Co., Ltd. Electrolysis copper-alloy foil, method of the same, electrolytic-solution using the production, negative electrode aggregation used the same, secondary battery, and electrode of the same
JP2018031072A (ja) * 2016-08-23 2018-03-01 エル エス エムトロン リミテッドＬＳ Ｍｔｒｏｎ Ｌｔｄ． 電解銅箔、それを含む電極、それを含む二次電池およびその製造方法
EP3309881A1 (en) * 2016-10-12 2018-04-18 Ls Mtron Ltd. Easily handleable electrolytic copper foil, electrode comprising the same, secondary battery comprising the same, and method for manufacturing the same
US9966608B2 (en) * 2011-06-30 2018-05-08 Furukawa Electric Co., Ltd. Electrolytic copper foil, method of producing electrolytic copper foil, lithium ion secondary cell using electrolytic copper foil as collector
JP2018111882A (ja) * 2017-01-13 2018-07-19 エル エス エムトロン リミテッドＬＳ Ｍｔｒｏｎ Ｌｔｄ． しわが実質的にない電解銅箔、それを含む電極、それを含む二次電池、およびその製造方法
US10218004B2 (en) 2015-06-26 2019-02-26 Kcf Technologies Co., Ltd. Electrolytic copper foil for lithium secondary battery and lithium secondary battery comprising the same
US20190100848A1 (en) * 2016-06-21 2019-04-04 Guangdong Guanghua Sci-Tech Co., Ltd. Copper Electroplating Solution and Copper Electroplating Process
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JP4583149B2 (ja) * 2004-12-01 2010-11-17 三井金属鉱業株式会社 電解銅箔及びその製造方法
KR100704685B1 (ko) * 2005-03-26 2007-04-06 한국기계연구원 메쉬형 회전 음극드럼 도금법에 의한 연속 금속메쉬 제조장치
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KR101733410B1 (ko) * 2016-11-11 2017-05-10 일진머티리얼즈 주식회사 저온 물성이 우수한 이차전지용 전해동박 및 그의 제조방법
JPWO2018207788A1 (ja) 2017-05-09 2020-05-14 Ｊｘ金属株式会社 電解銅箔及びその製造方法、銅張積層板、プリント配線板及びその製造方法、並びに電子機器及びその製造方法
CN112030199B (zh) * 2020-08-27 2021-11-12 江苏艾森半导体材料股份有限公司 一种用于先进封装的高速电镀铜添加剂及电镀液
CN112111761B (zh) * 2020-09-07 2021-09-21 浙江大学 一种高延伸率电解铜箔的电解液及其应用
CN112839436B (zh) * 2020-12-30 2022-08-05 广东嘉元科技股份有限公司 一种高频高速印制电路板用电解铜箔及其制备方法
CN112779569B (zh) * 2020-12-30 2022-01-18 铜陵市华创新材料有限公司 一种改善锂离子电池用电解铜箔激光模切熔珠的方法
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