WO2012121020A1 - 強度が高く、異常電着による突起形状が少ない電解銅箔及びその製造方法 - Google Patents
強度が高く、異常電着による突起形状が少ない電解銅箔及びその製造方法 Download PDFInfo
- Publication number
- WO2012121020A1 WO2012121020A1 PCT/JP2012/054383 JP2012054383W WO2012121020A1 WO 2012121020 A1 WO2012121020 A1 WO 2012121020A1 JP 2012054383 W JP2012054383 W JP 2012054383W WO 2012121020 A1 WO2012121020 A1 WO 2012121020A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- copper foil
- electrolytic
- groups
- electrolytic copper
- compound
- Prior art date
Links
Images
Classifications
-
- 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
-
- 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
- C25D1/00—Electroforming
-
- 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
-
- 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
Definitions
- the present invention relates to an electrolytic copper foil having a small surface roughness, a high strength, and a small protrusion shape due to abnormal electrodeposition and a method for producing the same, and more particularly to an electrolytic copper foil useful for a secondary battery negative electrode current collector.
- Electrolytic copper foil produced by electroplating greatly contributes to the development of electrical and electronic industries, and is indispensable as a printed circuit material and secondary battery negative electrode current collector.
- the manufacturing history of the electrolytic copper foil is old (see Patent Document 1 and Patent Document 2), but recently its usefulness as a secondary battery negative electrode current collector has been reconfirmed.
- An example of producing an electrolytic copper foil is as follows. For example, in an electrolytic cell, a titanium or stainless steel rotating drum having a diameter of about 3000 mm and a width of about 2500 mm and an electrode distance of about 5 mm around the drum are arranged. Deploy. Copper, sulfuric acid, and glue are introduced into this electrolytic cell to form an electrolytic solution. Then, the linear velocity, the electrolyte solution temperature, and the current density are adjusted, copper is deposited on the surface of the rotating drum, the copper deposited on the surface of the rotating drum is peeled off, and a copper foil is continuously produced.
- This electrolytic copper foil manufacturing method can reduce the manufacturing cost, and can manufacture from an extremely thin layer thickness of about several ⁇ m to a thick copper foil of about 70 ⁇ m, and one side of the electrolytic copper foil is moderate. Therefore, it has many advantages such as high adhesive strength with the resin.
- an electrolytic copper foil has been used as a copper foil for a battery negative electrode material for vehicles, and the strength of the electrolytic copper foil is required as its characteristics.
- the manufactured electrolytic copper foil has a characteristic that can meet this demand for high strength.
- a protrusion shape in which nucleus growth proceeds rapidly due to abnormal electrodeposition occurs at a density of 50 / cm 2 .
- the protrusion shape due to abnormal electrodeposition is a columnar protrusion shape having a height of 1.0 ⁇ m or more and a diameter of 4.0 ⁇ m or more.
- the height is 1.0 to 5 ⁇ m.
- the average distribution is 0.0 ⁇ m, 2.7 ⁇ m, the diameter is 4.0-20.0 ⁇ m, and the average is 9.8 ⁇ m.
- a typical protrusion shape by abnormal electrodeposition is shown in FIG. Further, the number of protrusion shapes due to abnormal electrodeposition was measured by observation with an electron microscope, and the height and size thereof were measured with a three-dimensional surface shape measuring device (manufactured by VEECO: NT1100).
- Protrusion shape due to abnormal electrodeposition is considered to be caused by the electrodeposition process that occurs in the manufacturing process of electrolytic copper foil.
- the shape of the protrusion due to abnormal electrodeposition does not directly affect the copper foil characteristics, but it must be reduced as much as possible.
- the present invention relates to an electrolytic copper foil having a small surface roughness, a high strength, and a small protrusion shape due to abnormal electrodeposition, and a method for producing the same, and particularly to provide an electrolytic copper foil useful for a secondary battery negative electrode current collector. Is an issue.
- the present application provides the following invention.
- the surface roughness Rz is 2.0 ⁇ m or less, the height is 1.0 ⁇ m or more, the diameter is 4.0 ⁇ m or more, and the number of protrusions formed by abnormal electrodeposition is 20 pieces / cm 2 or less.
- Electrolytic copper foil (2) The electrolytic copper foil according to (1), wherein the tensile strength is 45 to 70 kg / mm 2 .
- glue 2-5 mass ppm
- a compound having one or more epoxy groups in one molecule and an amine compound are added.
- the electrolytic solution temperature is set to 60 to 65 ° C.
- R1 and R2 are selected from the group consisting of hydroxyalkyl groups, ether groups, aryl groups, aromatic substituted alkyl groups, unsaturated hydrocarbon groups, and alkyl groups, and A is an epoxy compound. And n represents an integer of 1 or more.
- the electrolytic solution temperature is set to 60 to 65 ° C., 3.
- the present invention relates to an electrolytic copper foil having a high strength and a small protrusion shape due to abnormal electrodeposition and a method for producing the same, and particularly has an excellent effect of providing an electrolytic copper foil useful for a secondary battery negative electrode current collector. ing.
- FIG. 2 is a diagram showing an electron micrograph of a typical surface state of Example 1.
- FIG. It is a figure which shows the electron micrograph of the surface state of the comparative example 1 which does not contain the additive of the amine compound which has a specific skeleton shown by General formula (1), and an organic sulfur compound.
- the present invention provides an electrolytic copper foil that has few protrusion shapes due to abnormal electrodeposition and can exhibit high strength in the electrolytic copper foil.
- the electrolytic copper foil of the present invention is particularly useful as a copper foil for a secondary battery negative electrode current collector.
- glue 2 to 5 mass ppm
- an amine compound having a specific skeleton represented by general formula (1) obtained by addition reaction of a compound having one or more epoxy groups in one molecule and an amine compound
- Addition of organic sulfur compound By using an electrolytic solution containing 3 to 10 massppm, copper layer growth during the plating process is suppressed.
- the surface roughness is Rz: 2.0 ⁇ m or less
- the strength is 45 kgf / mm 2 to 70 kgf / mm 2
- the protrusion shape due to abnormal electrodeposition is 20
- the present invention provides an electrolytic copper foil reduced to a generation density of 1 piece / cm 2 .
- the copper layer is formed by the nucleation of grain boundaries and the progress of nucleation.
- the rate of nucleation is increased rather than nucleation, thereby forming a fine grain boundary and exhibiting low roughness and high strength characteristics.
- the generation rate of nucleation does not match the nucleation rate, and there is a problem that a protrusion shape due to abnormal electrodeposition is generated due to partial nucleation.
- the present invention is a specific skeleton represented by the general formula (1) obtained by addition reaction of a compound having one or more epoxy groups in the molecule and an amine compound, in addition to glue which is a conventional additive as an additive.
- the number of abnormal electrodeposited particles having an average particle size of 5 to 15 ⁇ m is 20 particles / cm 2 or less and the strength is 45 to 70 kg / to a mm 2
- the surface roughness to produce the following electrolytic copper foil Rz2.0 ⁇ m is glue: 2 ⁇ 5massppm, adding a first compound having one or more epoxy groups in the molecule and the amine compound
- the electrolytic solution temperature is set to 60 to 65 ° C., and the current Electrolysis with a density of 60 to 110 A / dm 2 is preferable.
- R1 and R2 are selected from the group consisting of a hydroxyalkyl group, an ether group, an aryl group, an aromatic substituted alkyl group, an unsaturated hydrocarbon group, and an alkyl group, and A is an epoxy compound.
- N represents an integer of 1 or more.
- the electrolytic copper foil of the present invention is produced by an electrolytic method using a sulfuric acid copper electrolytic solution.
- the present invention relates to a conventional electrolytic copper foil in which a rotating drum made of titanium or stainless steel having a diameter of about 3000 mm and a width of about 2500 mm and an electrode is disposed with a distance of about 5 mm around the drum in an electrolytic cell. It can manufacture using a manufacturing apparatus.
- the example of this apparatus is an example and there is no restriction
- Addition of 3 to 10 mass ppm of an amine compound having a specific skeleton represented by the general formula (1) obtained by addition reaction with an amine compound and an organic sulfur compound: 3 to 10 mass ppm is made to be an electrolytic solution.
- the linear velocity was adjusted to 1.5 to 5.0 m / s
- the electrolyte temperature was adjusted to 60 ° C. to 65 ° C.
- the current density was adjusted to 60 to 120 A / dm 2 to deposit copper on the surface of the rotating drum,
- the copper deposited on the surface of the rotating drum is peeled off to continuously produce a copper foil. That is, as described above, electrolysis at an electrolyte temperature of 60 to 65 ° C. and a current density of 60 to 120 A / dm 2 is a preferable condition for obtaining an electrolytic copper foil having the above characteristics. In particular, the adjustment of the electrolyte temperature is important. Details will be described in Examples and Comparative Examples.
- the average surface roughness Ra can be set to 0.04 to 0.20 ⁇ m. In this case, the reason why the lower limit of the average surface roughness Ra is 0.04 ⁇ m is to form fine particles and improve the adhesion.
- the reason for setting the upper limit to 0.20 ⁇ m is to reduce variation in weight thickness. Thereby, for example, the charge / discharge characteristics of the secondary battery can be improved.
- These surface roughnesses show an example and can be appropriately adjusted according to the use of the electrolytic copper foil.
- the average diameter of the roughened particles on the roughened surface be 0.1 to 0.4 ⁇ m. It is desired that the roughened particles are fine particles and the fine particles are more uniform. Similarly to the above, this is a preferable mode for improving the adhesion of the battery active material and applying as much active material as possible to increase the electric capacity of the battery.
- the maximum height of the roughened layer in the copper foil for the negative electrode current collector for the secondary battery is 0.2 ⁇ m or less. This is also a preferable mode for reducing the thickness variation of the roughening treatment layer, improving the adhesion of the battery active material, and increasing the electric capacity of the battery by applying as much active material as possible.
- the present invention can be managed and achieved based on an index that makes the thickness of the roughened particles 0.2 ⁇ m or less.
- the copper foil for a negative electrode current collector for a secondary battery can form one type of plating of copper, cobalt, nickel or two or more types of alloy plating as roughening particles. Usually, roughened particles are formed by three-part alloy plating of copper, cobalt, and nickel. Furthermore, the copper foil for the negative electrode current collector for the secondary battery has a cobalt-nickel alloy plating layer on the roughened surface on both the front and back sides of the rolled copper alloy foil in order to improve heat resistance and weather resistance (corrosion resistance). It is a desirable element to form one or more rust-proofing layers or heat-resistant layers and / or silane coupling layers selected from zinc-nickel alloy plating layers and chromate layers.
- the copper foil for a negative electrode current collector for a secondary battery of the present invention can reduce the thickness variation in the copper foil width direction of the rolled copper alloy foil after the front and back surface roughening treatment to 0.5% or less.
- An excellent copper foil for a negative electrode current collector for a secondary battery can be provided.
- the roughening treatment on the copper foil for the secondary battery negative electrode current collector of the present invention can be performed, for example, copper roughening treatment or copper-cobalt-nickel alloy plating treatment.
- the copper roughening treatment is as follows. Copper roughening treatment Cu: 10 to 25 g / L H 2 SO 4 : 20 to 100 g / L Temperature: 20-40 ° C Dk: 30 to 70 A / dm 2 Time: 1-5 seconds
- the roughening treatment by the copper-cobalt-nickel alloy plating treatment is as follows.
- electrolytic plating the amount of deposition is carried out to form a ternary alloy layer such that 15 ⁇ 40mg / dm 2 of copper -100 ⁇ 3000 ⁇ g / dm 2 of cobalt -100 ⁇ 500 ⁇ g / dm 2 of nickel.
- This ternary alloy layer also has heat resistance.
- the general bath and plating conditions for forming such ternary copper-cobalt-nickel alloy plating are as follows. (Copper-cobalt-nickel alloy plating) Cu: 10 to 20 g / liter Co: 1 to 10 g / liter Ni: 1 to 10 g / liter pH: 1 to 4 Temperature: 30-50 ° C Current density D k : 20 to 50 A / dm 2 Time: 1-5 seconds
- a cobalt-nickel alloy plating layer can be formed on the roughened surface.
- the cobalt-nickel alloy plating layer has a cobalt adhesion amount of 200 to 3000 ⁇ g / dm 2 and a cobalt ratio of 60 to 70 mass%.
- This treatment can be regarded as a kind of rust prevention treatment in a broad sense.
- a zinc-nickel alloy plating layer can be further formed on the cobalt-nickel alloy plating.
- the total amount of the zinc-nickel alloy plating layer is 150 to 500 ⁇ g / dm 2 and the nickel ratio is 16 to 40% by mass. This has the role of a heat and rust preventive layer.
- the conditions for zinc-nickel alloy plating are as follows. (Zinc-nickel alloy plating) Zn: 0-30 g / liter Ni: 0-25 g / liter pH: 3-4 Temperature: 40-50 ° C Current density D k : 0.5 to 5 A / dm 2 Time: 1 to 3 seconds
- a preferable antirust treatment is a coating treatment of chromium oxide alone or a mixture coating treatment of chromium oxide and zinc / zinc oxide.
- Chromium oxide and zinc / zinc oxide mixture film treatment is a method of forming zinc or zinc oxide comprising zinc oxide and chromium oxide by electroplating using a plating bath containing zinc salt or zinc oxide and chromate. It is the process which coat
- the plating bath typically, at least one kind of dichromate such as K 2 Cr 2 O 7 and Na 2 Cr 2 O 7 and CrO 3 and a water-soluble zinc salt such as ZnO 4 and ZnSO 4 ⁇ 7H are used.
- a mixed aqueous solution of at least one kind such as 2 O and an alkali hydroxide is used.
- a typical plating bath composition and electrolysis conditions are as follows. The copper foil thus obtained has excellent heat resistance peel strength, oxidation resistance and hydrochloric acid resistance.
- Chromium rust prevention treatment K 2 Cr 2 O 7 (Na 2 Cr 2 O 7 or CrO 3 ): 2 to 10 g / liter NaOH or KOH: 10 to 50 g / liter ZnO or ZnSO 4 ⁇ 7H 2 O: 0.05 to 10 g / liter pH: 3-13 Bath temperature: 20-80 ° C Current density D k : 0.05 to 5 A / dm 2 Time: 5-30 seconds Anode: Pt—Ti plate, stainless steel plate, etc. Chromium oxide requires a coating amount of 15 ⁇ g / dm 2 or more, and zinc requires a coating amount of 30 ⁇ g / dm 2 or more.
- silane treatment is performed by applying a silane coupling agent to at least the roughened surface on the rust preventive layer, mainly for the purpose of improving the adhesion between the copper foil and the resin substrate.
- a silane coupling agent used for the silane treatment include olefin silane, epoxy silane, acrylic silane, amino silane, and mercapto silane, which can be appropriately selected and used. .
- Application method may be any of spraying a silane coupling agent solution by spraying, coating with a coater, dipping, pouring and the like.
- Japanese Patent Publication No. 60-15654 describes that the adhesion between a copper foil and a resin substrate is improved by subjecting the rough surface of the copper foil to a chromate treatment followed by a silane coupling agent treatment. . Refer to this for details. Thereafter, if necessary, an annealing treatment may be performed for the purpose of improving the ductility of the copper foil.
- Example 1 In the electrolytic cell, a rotating drum made of titanium having a diameter of about 3133 mm and a width of 2476.5 mm and an electrode distance of about 5 mm are arranged around the drum.
- copper concentration: 90 g / L, sulfuric acid concentration: 80 g / L, glue concentration: 3 ppm, and an additive of an amine compound and an organic sulfur compound having a specific skeleton represented by the general formula (1): 10 mass ppm was used as an electrolytic solution.
- the linear velocity was adjusted to 3.0 m / s, the electrolyte temperature: 60 ° C., and the current density: 84 A / dm 2 , copper was deposited on the surface of the rotating drum, and the copper deposited on the surface of the rotating drum was peeled off.
- the copper foil was continuously manufactured.
- Example 2 In the electrolytic cell, a rotating drum made of titanium having a diameter of about 3133 mm and a width of 2476.5 mm and an electrode distance of about 5 mm are arranged around the drum.
- copper concentration: 90 g / L, sulfuric acid concentration: 80 g / L, glue concentration: 3 ppm, and an additive of an amine compound having a specific skeleton represented by the general formula (1) and an organic sulfur compound: 5 mass ppm was used as an electrolytic solution.
- the linear velocity is adjusted to 3.0 m / s
- the electrolyte temperature is 63 ° C.
- the current density is 84 A / dm 2
- copper is deposited on the surface of the rotating drum, and the copper deposited on the surface of the rotating drum is peeled off.
- the copper foil was continuously manufactured.
- the electrolytic copper foil thus produced was examined for strength (normal tensile strength), Rz surface roughness, and the number of protrusion shapes due to abnormal electrodeposition.
- the strength (normal tensile strength) was 59.3 kgf / mm 2
- the Rz surface roughness was 1.4 ⁇ m
- the number of protrusion shapes due to abnormal electrodeposition was 8 / cm 2 . All satisfied the conditions of the present invention.
- Example 3 In the electrolytic cell, a rotating drum made of titanium having a diameter of about 3133 mm and a width of 2476.5 mm and an electrode distance of about 5 mm are arranged around the drum.
- copper concentration: 90 g / L, sulfuric acid concentration: 80 g / L, glue concentration: 3 ppm, and an additive of an amine compound and an organic sulfur compound having a specific skeleton represented by the general formula (1): 3 mass ppm was used as an electrolytic solution.
- the linear velocity is adjusted to 3.0 m / s
- the electrolyte temperature is 63 ° C.
- the current density is 109 A / dm 2
- copper is deposited on the surface of the rotating drum, and the copper deposited on the surface of the rotating drum is peeled off.
- the copper foil was continuously manufactured.
- the electrolytic copper foil thus produced was examined for strength (normal tensile strength), Rz surface roughness, and the number of protrusion shapes due to abnormal electrodeposition.
- the strength (normal tensile strength) was 57.0 kgf / mm 2
- the Rz surface roughness was 1.3 ⁇ m
- the number of protrusion shapes due to abnormal electrodeposition was 12 / cm 2 . All satisfied the conditions of the present invention.
- the linear velocity is adjusted to 3.0 m / s
- the electrolyte temperature is 57 ° C.
- the current density is 84 A / dm 2
- copper is deposited on the surface of the rotating drum, and the copper deposited on the surface of the rotating drum is peeled off.
- the copper foil was continuously manufactured.
- the linear velocity is adjusted to 3.0 m / s
- the electrolyte temperature is 57 ° C.
- the current density is 97 A / dm 2
- copper is deposited on the surface of the rotating drum, and the copper deposited on the surface of the rotating drum is peeled off.
- the copper foil was continuously manufactured.
- the present invention can provide an electrolytic copper foil having a high normal tensile strength and a surface roughness Rz of 2.0 ⁇ m or less, and further can provide an electrolytic copper foil having a small number of protrusions by abnormal electrodeposition. This is useful for an electrolytic copper foil for a negative electrode current collector.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
Description
この電解槽の中に、銅、硫酸、にかわを導入して電解液とする。そして、線速、電解液温、電流密度を調節し、回転ドラムの表面に銅を析出させ、回転ドラムの表面に析出した銅を剥ぎ取り、連続的に銅箔を製造している。
代表的な異常電着による突起形状を図1に示す。また、異常電着による突起形状の数量は電子顕微鏡観察にて計測し、その高さ及びサイズは3次元表面形状測定装置(VEECO社製:NT1100)にて計測したものである。
(1)表面粗さRz2.0μm以下であり、高さが1.0μm以上、直径が4.0μm以上である異常電着による突起形状の個数が20個/cm2以下であることを特徴とする電解銅箔。
(2)抗張力が45~70kg/mm2であることを特徴とする前記(1)記載の電解銅箔。
(3)二次電池負極集電体用銅箔であることを特徴とする前記(1)又は(2)記載の電解銅箔。
(5)硫酸系銅電解液を用いた電解法により電解銅箔を製造する方法であって、にかわ:2~5massppm、1分子中に1個以上のエポキシ基を有する化合物とアミン化合物とを付加反応させることにより得られる下記一般式(1)で示す特定骨格を有するアミン化合物と有機硫黄化合物の添加剤:3~10massppmを含む電解液を用いて、電解液温度を60~65°Cとし、電流密度を60~120A/dm2として電解することにより、請求項1又は2記載の電解銅箔を製造することを特徴とする電解銅箔の製造方法。
具体的には、にかわ:2~5massppm、1分子中に1個以上のエポキシ基を有する化合物とアミン化合物とを付加反応させることにより得られる一般式(1)で示す特定骨格を有するアミン化合物と有機硫黄化合物の添加剤:3~10massppmを含む電解液を用いることでメッキ過程での銅層成長を抑制する。
すなわち、これによって異常電着を抑制することができ、表面粗さがRz:2.0μm以下であり、45kgf/mm2~70kgf/mm2の高強度でありかつ異常電着による突起形状を20個/cm2の発生密度に低減した電解銅箔を提供するものである。
すなわち、上記の通り、電解液温度を60~65°Cとし、電流密度を60~120A/dm2として電解することが、上記の特性を有する電解銅箔を得る好適な条件である。特に電解液温の調整は重要である。詳細は、実施例及び比較例で説明する。
例えば、銅の粗化処理は、次の通りである。
銅粗化処理
Cu: 10~25g/L
H2SO4: 20~100g/L
温度: 20~40°C
Dk: 30~70A/dm2
時間: 1~5秒
(銅-コバルト-ニッケル合金めっき)
Cu:10~20g/リットル
Co:1~10g/リットル
Ni:1~10g/リットル
pH:1~4
温度:30~50°C
電流密度Dk :20~50A/dm2
時間:1~5秒
(コバルト-ニッケル合金めっき)
Co:1~20g/リットル
Ni:1~20g/リットル
pH:1.5~3.5
温度:30~80°C
電流密度Dk :1.0~20.0A/dm2
時間:0.5~4秒
(亜鉛-ニッケル合金めっき)
Zn:0~30g/リットル
Ni:0~25g/リットル
pH:3~4
温度:40~50°C
電流密度Dk :0.5~5A/dm2
時間:1~3秒
K2Cr2O7(Na2Cr2O7或いはCrO3):2~10g/リットル
NaOH或いはKOH :10~50g/リットル
ZnO 或いはZnSO4・7H2O:0.05~10g/リットル
pH:3~13
浴温:20~80°C
電流密度Dk :0.05~5A/dm2
時間:5~30秒
アノード:Pt-Ti 板、ステンレス鋼板等
クロム酸化物はクロム量として15μg/dm2以上、亜鉛は30μg/dm2以上の被覆量が要求される。
電解槽の中に、直径約3133mm、幅2476.5mmのチタン製の回転ドラムと、ドラムの周囲に5mm程度の極間距離を置いて電極を配置する。この電解槽の中に、銅濃度:90g/L、硫酸濃度:80g/L、にかわ濃度:3ppm、さらに前記一般式(1)で示す特定骨格を有するアミン化合物と有機硫黄化合物の添加剤:10massppmを導入して電解液とした。
そして、線速:3.0m/s、電解液温:60°C、電流密度:84A/dm2に調節し、回転ドラムの表面に銅を析出させ、回転ドラムの表面に析出した銅を剥ぎ取り、連続的に銅箔を製造した。
いずれも本願発明の条件を満足していた。また、代表的な表面状態の電子顕微鏡写真を図2に示す。図2より、明らかに異常電着による突起形状の発生が抑制されていることが確認できる。以下の実施例及び比較例の、結果も表1に示す。
電解槽の中に、直径約3133mm、幅2476.5mmのチタン製の回転ドラムと、ドラムの周囲に5mm程度の極間距離を置いて電極を配置する。この電解槽の中に、銅濃度:90g/L、硫酸濃度:80g/L、にかわ濃度:3ppm、さらに前記一般式(1)で示す特定骨格を有するアミン化合物と有機硫黄化合物の添加剤:5massppmを導入して電解液とした。そして、線速:3.0m/s、電解液温:63°C、電流密度:84A/dm2に調節し、回転ドラムの表面に銅を析出させ、回転ドラムの表面に析出した銅を剥ぎ取り、連続的に銅箔を製造した。
いずれも本願発明の条件を満足していた。
電解槽の中に、直径約3133mm、幅2476.5mmのチタン製の回転ドラムと、ドラムの周囲に5mm程度の極間距離を置いて電極を配置する。この電解槽の中に、銅濃度:90g/L、硫酸濃度:80g/L、にかわ濃度:3ppm、さらに前記一般式(1)で示す特定骨格を有するアミン化合物と有機硫黄化合物の添加剤:3massppmを導入して電解液とした。
そして、線速:3.0m/s、電解液温:63°C、電流密度:109A/dm2に調節し、回転ドラムの表面に銅を析出させ、回転ドラムの表面に析出した銅を剥ぎ取り、連続的に銅箔を製造した。
いずれも本願発明の条件を満足していた。
電解槽の中に、直径約3133mm、幅2476.5mmのチタン製の回転ドラムと、ドラムの周囲に5mm程度の極間距離を置いて電極を配置する。この電解槽の中に、銅濃度:90g/L、硫酸濃度:80g/L、にかわ濃度:3ppm、さらに前記一般式(1)で示す特定骨格を有するアミン化合物と有機硫黄化合物の添加剤:0massppmを導入して電解液とした。
そして、線速:3.0m/s、電解液温:57°C、電流密度:84A/dm2に調節し、回転ドラムの表面に銅を析出させ、回転ドラムの表面に析出した銅を剥ぎ取り、連続的に銅箔を製造した。
いずれも本願発明の条件を満足していなかった。また、代表的な表面状態の電子顕微鏡写真を図3に示す。図3より、前記一般式(1)で示す特定骨格を有するアミン化合物と有機硫黄化合物の添加剤を含有していない状態では、異常電着による突起形状が発生しやすい状態であることが確認できる。
電解槽の中に、直径約3133mm、幅2476.5mmのチタン製の回転ドラムと、ドラムの周囲に5mm程度の極間距離を置いて電極を配置する。この電解槽の中に、銅濃度:90g/L、硫酸濃度:80g/L、にかわ濃度:3ppm、さらに前記一般式(1)で示す特定骨格を有するアミン化合物と有機硫黄化合物の添加剤:1massppmを導入して電解液とした。
そして、線速:3.0m/s、電解液温:57°C、電流密度:97A/dm2に調節し、回転ドラムの表面に銅を析出させ、回転ドラムの表面に析出した銅を剥ぎ取り、連続的に銅箔を製造した。
いずれも本願発明の条件を満足していなかった。
Claims (5)
- 表面粗さRz2.0μm以下であり、高さは1.0μm以上、径は4.0μm以上である異常電着による突起形状の個数が20個/cm2以下である、ことを特徴とする電解銅箔。
- 抗張力が45~70kg/mm2であることを特徴とする請求項1記載の電解銅箔。
- 二次電池負極集電体用銅箔であることを特徴とする請求項1記載の電解銅箔。
- 硫酸系銅電解液を用いた電解法により電解銅箔を製造する方法であって、にかわ:2~5massppm、1分子中に1個以上のエポキシ基を有する化合物とアミン化合物とを付加反応させることにより得られる下記一般式(1)で示す特定骨格を有するアミン化合物と有機硫黄化合物の添加剤:3~10massppmを含む電解液を用いて、電解液温度を60~65°Cとし、電流密度を60~120A/dm2として電解することを特徴とする電解銅箔の製造方法。
- 硫酸系銅電解液を用いた電解法により電解銅箔を製造する方法であって、にかわ:2~5massppm、1分子中に1個以上のエポキシ基を有する化合物とアミン化合物とを付加反応させることにより得られる下記一般式(1)で示す特定骨格を有するアミン化合物と有機硫黄化合物の添加剤:3~10massppmを含む電解液を用いて、電解液温度を60~65°Cとし、電流密度を60~120A/dm2として電解することにより、請求項1又は2記載の電解銅箔を製造することを特徴とする電解銅箔の製造方法。
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013503449A JPWO2012121020A1 (ja) | 2011-03-04 | 2012-02-23 | 強度が高く、異常電着による突起形状が少ない電解銅箔及びその製造方法 |
KR1020137022228A KR20130117865A (ko) | 2011-03-04 | 2012-02-23 | 강도가 높고, 이상 전착에 의한 돌기 형상이 적은 전해 구리박 및 그 제조 방법 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011047631 | 2011-03-04 | ||
JP2011-047631 | 2011-03-04 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012121020A1 true WO2012121020A1 (ja) | 2012-09-13 |
Family
ID=46797989
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2012/054383 WO2012121020A1 (ja) | 2011-03-04 | 2012-02-23 | 強度が高く、異常電着による突起形状が少ない電解銅箔及びその製造方法 |
Country Status (4)
Country | Link |
---|---|
JP (1) | JPWO2012121020A1 (ja) |
KR (1) | KR20130117865A (ja) |
TW (1) | TW201247940A (ja) |
WO (1) | WO2012121020A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014070263A (ja) * | 2012-09-28 | 2014-04-21 | Jx Nippon Mining & Metals Corp | 電解銅箔及び電解銅箔の製造方法 |
JP2023512132A (ja) * | 2020-12-30 | 2023-03-24 | 広東嘉元科技股▲ふん▼有限公司 | 高周波・高速プリント回路基板用電解銅箔とその調製方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10330983A (ja) * | 1997-05-30 | 1998-12-15 | Fukuda Metal Foil & Powder Co Ltd | 電解銅箔及びその製造方法 |
JP2002294481A (ja) * | 2001-03-29 | 2002-10-09 | Mitsui Mining & Smelting Co Ltd | 金属箔電解製造装置 |
JP2004107786A (ja) * | 2002-07-23 | 2004-04-08 | Nikko Materials Co Ltd | 特定骨格を有するアミン化合物及び有機硫黄化合物を添加剤として含む銅電解液並びにそれにより製造される電解銅箔 |
JP2009004423A (ja) * | 2007-06-19 | 2009-01-08 | Hitachi Cable Ltd | キャリア箔付き銅箔 |
JP2009293103A (ja) * | 2008-06-09 | 2009-12-17 | Nippon Denkai Kk | 支持体付極薄銅箔及びその製造方法 |
-
2012
- 2012-02-23 WO PCT/JP2012/054383 patent/WO2012121020A1/ja active Application Filing
- 2012-02-23 JP JP2013503449A patent/JPWO2012121020A1/ja not_active Abandoned
- 2012-02-23 KR KR1020137022228A patent/KR20130117865A/ko not_active Application Discontinuation
- 2012-02-24 TW TW101106185A patent/TW201247940A/zh unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10330983A (ja) * | 1997-05-30 | 1998-12-15 | Fukuda Metal Foil & Powder Co Ltd | 電解銅箔及びその製造方法 |
JP2002294481A (ja) * | 2001-03-29 | 2002-10-09 | Mitsui Mining & Smelting Co Ltd | 金属箔電解製造装置 |
JP2004107786A (ja) * | 2002-07-23 | 2004-04-08 | Nikko Materials Co Ltd | 特定骨格を有するアミン化合物及び有機硫黄化合物を添加剤として含む銅電解液並びにそれにより製造される電解銅箔 |
JP2009004423A (ja) * | 2007-06-19 | 2009-01-08 | Hitachi Cable Ltd | キャリア箔付き銅箔 |
JP2009293103A (ja) * | 2008-06-09 | 2009-12-17 | Nippon Denkai Kk | 支持体付極薄銅箔及びその製造方法 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2014070263A (ja) * | 2012-09-28 | 2014-04-21 | Jx Nippon Mining & Metals Corp | 電解銅箔及び電解銅箔の製造方法 |
JP2023512132A (ja) * | 2020-12-30 | 2023-03-24 | 広東嘉元科技股▲ふん▼有限公司 | 高周波・高速プリント回路基板用電解銅箔とその調製方法 |
Also Published As
Publication number | Publication date |
---|---|
JPWO2012121020A1 (ja) | 2014-07-17 |
KR20130117865A (ko) | 2013-10-28 |
TW201247940A (en) | 2012-12-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5417458B2 (ja) | 二次電池負極集電体用銅箔 | |
JP5148726B2 (ja) | 電解銅箔及び電解銅箔の製造方法 | |
JP5074611B2 (ja) | 二次電池負極集電体用電解銅箔及びその製造方法 | |
TWI245082B (en) | Electrolyte solution for manufacturing electrolytic copper foil and electrolytic copper foil manufacturing method using the same | |
US9595719B2 (en) | Composite metal foil and production method therefor | |
WO2012169249A1 (ja) | 液晶ポリマー銅張積層板及び当該積層板に用いる銅箔 | |
WO2012137613A1 (ja) | 多孔質金属箔およびその製造方法 | |
JP2012172198A (ja) | 電解銅箔及びその製造方法 | |
JP5822928B2 (ja) | 強度が高く、かつ反りの少ない電解銅箔及びその製造方法 | |
TWI633196B (zh) | 附有銅鍍層的壓延銅箔 | |
Duhin et al. | Electroless plating of rhenium–nickel alloys | |
JP5941959B2 (ja) | 電解銅箔及びその製造方法 | |
WO2012121020A1 (ja) | 強度が高く、異常電着による突起形状が少ない電解銅箔及びその製造方法 | |
WO2014033917A1 (ja) | 電解銅箔及びその製造方法 | |
JP5728118B1 (ja) | 表面処理銅箔、該表面処理銅箔の製造方法、および該表面処理銅箔を用いた銅張積層板 | |
JP4948656B2 (ja) | 二次電池集電体用穴あき粗化処理銅箔、その製造方法及びリチウムイオン二次電池負極電極 | |
WO2013150640A1 (ja) | 電解銅箔及びその製造方法 | |
TW201410922A (zh) | 強度高且由異常電沉積所導致之突起形狀少之電解銅箔及其製造方法 | |
JP2014070263A (ja) | 電解銅箔及び電解銅箔の製造方法 | |
KR101263072B1 (ko) | 초음파를 이용한 전기아연도금 강판의 제조방법 | |
TW201341594A (zh) | 電解銅箔及其製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 12754450 Country of ref document: EP Kind code of ref document: A1 |
|
DPE1 | Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101) | ||
ENP | Entry into the national phase |
Ref document number: 2013503449 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20137022228 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 12754450 Country of ref document: EP Kind code of ref document: A1 |