GB2320724A - Method for producing metal foil by electroforming - Google Patents

Method for producing metal foil by electroforming Download PDF

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Publication number
GB2320724A
GB2320724A GB9727198A GB9727198A GB2320724A GB 2320724 A GB2320724 A GB 2320724A GB 9727198 A GB9727198 A GB 9727198A GB 9727198 A GB9727198 A GB 9727198A GB 2320724 A GB2320724 A GB 2320724A
Authority
GB
United Kingdom
Prior art keywords
cathode
foil
metal foil
surface roughness
metal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
GB9727198A
Other versions
GB9727198D0 (en
Inventor
Katsunori Yamada
Kazuhiko Hashimoto
Hisanori Manabe
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fukuda Metal Foil and Powder Co Ltd
Original Assignee
Fukuda Metal Foil and Powder Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fukuda Metal Foil and Powder Co Ltd filed Critical Fukuda Metal Foil and Powder Co Ltd
Publication of GB9727198D0 publication Critical patent/GB9727198D0/en
Publication of GB2320724A publication Critical patent/GB2320724A/en
Withdrawn legal-status Critical Current

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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
    • H01M4/662—Alloys
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • 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
    • H01M4/669—Steels
    • 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

A metal foil 1 is produced by passing an electric current between a cathode 5 and an anode 4 immersed in a metal ion-containing electrolyte 3 to form a thin metal film on the surface of the cathode 5 and subsequently releasing the metal film 1 from the cathode 5. The cathode 5 has a surface roughness of not more than 0.8~m, and the surface of cathode is preferably made of Ti, a Ti alloy, stainless steel, Cr, a Cr alloy or Cr-plated steel. The electrodeposited metal film is preferably formed of copper or nickel. The cathode surface may be polished mechanically or chemically to reduce the surface roughness. The foil produced may be used as a current collector of a secondary battery.

Description

NETHOD FOR PRODUCING METAL FOIL This invention relates to a metal foil having pores, which can be used for example as a filter, a printing screen, an electromagnetic wave shield, or a current collector in a secondary battery.
There are metal foils having fine pores so far reported such as (1) one having a number of pores in a prescribed pattern, (2) one having three-dimensional pores at a high porosity with no prescribed pattern, and (3) one having fine pores at a high density (l) There are methods to produce a metal foil having a number of pores in a prescribed pattern such as (A) a method in which a rolled or electrodeposited metal foil having no pores is perforated by etching, punching, drilling etc, (B) a method in which non-plated pattern is formed on an insulating substrate by using an insulating substrate such as a photoresist., and thereafter an electrodeposited foil is obtained, (C) a method in which a prescribed pattern corresponding to the area not to be plated on an electrically conductive substrate is formed by using an insulating material such as a photoresist, and thereafter an electrodeposited foil is obtained, and (D) a method in which concave portions are provided on an electrically conductive substrate, the concave portions are filled with an insulating material to form a nonplated pattern, and thereafter an electrodeposited foil is obtained. The metal foil (1) having fine pores obtained by these methods are chiefly used as a filter or a printing screen.
(2) There is foamed nickel as a metal foil having three-dimensional pores at high porosity, which is mainly used for an electrode of a battery. The foamed nickel is produced by electroplating with nickel a foamed urethane substrate having been rendered electrically conductive, followed by heat treatment.
(3) The metal foil having fine pores at a high density is disclosed in Unexamined Japanese Patent Publication (kokai) No. Hei. 8-236120, etc. for use in a secondary battery.
According to the disclosure, a cathode is subjected to anodizing/oxidizing treatment and then electroplated with copper or nickel to produce porous electrodeposited copper or nickel foil.
The methods for producing the metal foil (1) involve many stepsr incurring the cost, and are unsuitable for mass production, or raise a problem as disposal of etching waste liquid. The method for producing the metal foil (2) also involves many steps and is not applicable to production of thin metal foil. The method for producing the metal foil (3) is simpler and expected to be suitable for mass ..production.
However, the resulting foil is disadvantageous n that its surface on the cathode side (S surface) and its surface on the opposite side (M surface) greatly differ in surface roughness.
According to this invention a method for producing a metal foil having fine pores comprises the steps of: applying an electric current between a cathode and an anode immersed in a metal ion-containing electrolyte to form a thin metal on a surface of the cathode; and releasing said metal film from said cathode to obtain a metal foil; wherein said cathode has a surface roughness (Rz) of not more than 0.8cm.
According to the present invention, it is possible to produce electrodeposited metal foil having fine pores and the similar surface roughness on the S and M surfaces thereof. It is also applicable to mass production without problems such as disposal of etching waste liquid, or an increase in the number of steps or of cost.
In the accompanying drawings, Figure 1 schematically illustrates an apparatus for producing electrodeposited metal foil.
Detailed description of the present invention will be described as follows.
The present invention provides a method for producing a metal foil having fine pores in which an electric current is applied between an anode immersed in an metal ion-containing electrolyte and a cathode, whose surface roughness Rz is not more than 0.8cm, mainly composed of titanium, a titanium alloy, stainless steel, chromium, a chromium alloy or chromium-plated steel to produce a metal thin film on the cathode, and thereafter, the metal layer is peeled to produce a metal foil having fine pores.
The present invention relates to a method for producing a metal foil having fine pores by electrodeposition, which will be described in detail.
In general, electrodeposited metal foil is produced as follows.
An electric current is applied between a rotating drum (cathode) made of titanium, stainless steel, chromium, chromium-plated steel, etc. and an anode 4 which is immersed in an electrolyte 3 containing an metal ion to thereby form a thin film of the metal on the rotating drum surface. Then, the metal film 1 is stripped off the drum 5 and wound in coil-shape 9. The thus obtained metal foil 1 has two different surfaces; a growth surface which has been in contact with-the plating bath (referred to an M surface) and a glossy surface which has been in contact with the cathode (referred to an S surface). The M surface has a matte appearance, while the S surface is a replica of the cathode surface, having semigloss or a metallic luster. The surface roughness of the S surface is substantially the same as that of the cathode surface.
The electrodeposited metal foil thus produced sometimes suffers from pinholes, one of the serious defects of metal foil. Because the pinholes have their origin in the thin oxide layer of the cathode surface, the cathode surface is polished with a polishing pad periodically or continuously. The polished surface profile of the cathode usually shows uniform roughness, giving semigloss or a metallic luster. The surface roughness Rz of the polished cathode surface is usually 1 to 3 Wm. Electrodeposited metal foil formed on such a polished cathode usually has a surface roughness Rz of 3 to 15 wm on the M surface and of 1 to 3 Wm on the S surface, while depending on the~foil thickness.
We, the inventors of the present invention, have noted the surface profile of the cathode surface and conducted extensive studies on cathodes polished to a varied degree of surface roughness. As a result, we have found that, when in using a cathode having a surface roughness Rz of not greater than 0.8Cun in electrode deposition, there is obtained electrodeposited metal foil which has fine pores, and whose M and S surfaces have similar surface roughness, i.e., the surface roughness Rz on the M surface ranging from 3 to 20cm, while that on the S surface ranging from 3 to 15Cun. It has also turned out that, in using a cathode whose surface roughness Rz is greater than 0.8 Wm, the resulting metal foil is not porous or, if porous, the pores are very scarce in number.
While the smoothness of the cathode surface is not particularly limited, the practical lower limit of the surface roughness Rz is preferably 0.01 Wm taking labor and cost of polishing into consideration.
The metal foil having fine pores produced by the method of the present invention has about 10 to 300 pores per mm2, and the pores have an irregular shape having a diameter varying from about 0.1 to 100 Clam. The shapes and arrangement of pores are irregular.
The electrolysis apparatus, the anode, and the electrolyte to be used in the practice of the present invention can be similar to the conventional one. For example, the electrolysis apparatus shown in Figure can be used. The anode includes insoluble electrodes of lead or platinum. A commonly used sulfuric acid-acidic bath containing 200 to 350 gIl of copper sulfate pentahydrate, 50 to 250 g/l of sulfuric acid, and small amounts of additives can be used as an electrolyte for the production of electrodeposited copper foil. Watts bath or a sulfamic acid bath can be used for the production of electrodeposited nickel foil as usual.
Materials of the cathode include titanium, a titanium alloy, stainless steel, chromium, a chromium alloy or chromiumplated steel. The manner of polishing the cathode surface to reduce the surface roughness Rz to 0.8 Wm or less is not particularly restricted, and generally employed mechanical or chemical polishing methods can be used. For example, mechanical polishing is carried out using emery paper, waterresistant abrasive paper, nylon nonwoven cloth impregnated with alumina or silicon carbide abrasive grains, and loose alumina abrasive grains.
The resulting electrodeposited metal foil can be used as a filter, an electromagnetic wave shield, a current collector of a secondary battery, and the like. In applications where adhesion is required, one or both sides or the foil can be made roughened in a known manner. For example, various single- or doubled-sided treatments for preparing copper foil are described in Examined Japanese Patent Publication Nos. Sho. 45-34245 and Sho. 50-40109.
EXAMPLES The present invention will now be described in greater detail with reference to the following Examples.
EXAMPLE 1 Electrodeposited copper foil having a thickness of 18 wm was produced by using a titanium cathode which had been polished with alumina grains to a surface roughness Rz of 0.70 im and an electrolyte containing 250 g/l of copper sulfate pentahydrate, 100 g/l of sulfuric acid, 2 ppm of glue, and 50 ppm of C1 ion at a solution temperature of 400C and a current density of 10 A/dm2. The appearance of the resulting copper foil was observed with the naked eye and under a microscope. As a result, the foil had 100 to 300 pores per mm2, a pore size of 0.1 to 20 gm, and a surface roughness Rz of 13 gm on the M surface and 9 Wm on the S surface.
EXAMPLE 2 Electrodeposited copper foil having a thickness of 18 gm was produced under the same conditions as in Example 1, except for using a stainless steel cathode which had been polished with alumina grains to a surface roughness Rz of 0.05 gm. The appearance of the resulting copper foil was observed in the same manner as in Example 1. As a result, the foil had 50 to 150 pores per mm2, a pore size of 0.1 to 10 gm, and a surface roughness Rz of 12 zm on the M surface and 10 wm on the S surface.
EXAMPLE 3 Electrodeposited copper foil having a thickness of 18 pin was produced under the same conditions as in Example 1, except for using a chromium cathode which had been polished with alumina grains to a surface roughness Rz of 0.73 pin. The appearance of the resulting copper foil was observed in the same manner as in Example 1. As a result, the foil had 10 to 100 pores per mm2, a pore size of 0.1 to 10 pin, and a surface roughness Rz of 12 pin on the M surface and 8 pin on the S surface.
EXAMPLE 4 Electrodeposited copper foil having a thickness of 18 pin was produced under the same conditions as in Example 1, except for using a chromium-plated steel cathode which had been polished with alumina grains to a surface roughness Rz of 0.45 pin. The appearance of the resulting copper foil was observed in the same manner as in Example 1. As a result, the foil had 20 to 150 pores per mm2, a pore size of 0.1 to 10 pin, and a surface roughness Rz of 15 pin on the M surface and 12 pin on the S surface.
EXAMPLE 5 Electrodeposited nickel foil having a thickness of 18 pin was produced by using a chromium cathode which had been polished with alumina grains to a surface roughness Rz of 0.24 pin and an electrolyte comprising 250 gIl of nickel sulfate and 40 g/l of boric acid at a solution temperature of 550C and a current density of 5 A/dm2. The appearance of the resulting nickel foil. was observed in the same manner as in Example 1.
As a result, the foil had 10 to 100 pores per mmZ, a pore size of 0.1 to 10 pin, and a surface roughness Rz of 5 pin on the M surface and 3 pin on the S surface.
COMPARATIVE EXAMPLE 1 Electrodeposited copper foil having a thickness of 18 pin was produced under the same conditions as in Example 1, except for using a titanium cathode which had been polished with alumina grains to a surface roughness Rz of 0.88 pin. The appearance of the resulting copper foil was observed in the same manner as in Example 1. As a result, the foil had 0 to 5 pores per mm2, a pore size of 0.1 to 50 pin, and a surface roughness Rz of 12 pin on the M surface and 7 pin on the S surface.
COMPARATIVE EXAMPLE 2 Electrodeposited copper foil having a thickness of 18 pin was produced under the same conditions as in Example 1, except for using a titanium cathode which had been polished with #1500 water-resistant abrasive paper to a surface roughness Rz of 1.52 pin. The appearance of the resulting copper foil was observed in the same manner as in Example 1.
As a result, the foil had no pores and a surface roughness Rz of 7 pin on the M surface and 3 pin on the S surface.

Claims (8)

1. A method for producing a metal foil having fine pores comprising the steps of: applying an electric current between a cathode and an anode immersed in a metal ion-containing electrolyte to form a thin metal film on a surface of the cathode; and releasing said metal film from said cathode to obtain a metal foil; wherein said cathode has a surface roughness (Rz) of not more than 0.8 pin.
2. A method according to claim 1, wherein the surface of said cathode comprises one of titanium, a titanium alloy, stainless steel, chromium, a chromium alloy or chromium-plated steel.
3. A method according to claim 1 or 2, wherein said cathode has the surface roughness of not less than 0.01cm.
4. A method according to any one of the preceding claims, 2 wherein said metal foil has 10 to 300 pores per mm
5. A method according to any one of the preceding claims, wherein said metal foil has pores having a diameter from 0.1 to 100 ym.
6. A method according to any one of the preceding claims, wherein said metal foil has a surface roughness (Rz) in the range of 3 to 20 Hm on the M surface and in the range of 3 to 15 ym on the S surface.
7. A method of making a foil substantially as described excluding the references to the comparative examples.
8. A foil made by a method in accordance with any one of the preceding claims.
GB9727198A 1996-12-27 1997-12-23 Method for producing metal foil by electroforming Withdrawn GB2320724A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP8349269A JPH10195689A (en) 1996-12-27 1996-12-27 Manufacture of finely perforated metallic foil

Publications (2)

Publication Number Publication Date
GB9727198D0 GB9727198D0 (en) 1998-02-25
GB2320724A true GB2320724A (en) 1998-07-01

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GB (1) GB2320724A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100365849C (en) * 2002-11-29 2008-01-30 三井金属矿业株式会社 Negative electrode for nonaqueous secondary battery, process of producing the negative electrode, and nonaqueous secondary battery
US8497026B2 (en) 2009-12-04 2013-07-30 Mitsui Mining & Smelting Co., Ltd. Porous metal foil and production method therefor
WO2014098774A1 (en) * 2012-12-21 2014-06-26 Agency For Science, Technology And Research Porous metallic membrane
US8980438B2 (en) 2011-04-08 2015-03-17 Mitsui Mining & Smelting Co., Ltd. Porous metal foil and production method therefor
US9512527B2 (en) 2011-01-13 2016-12-06 Mitsui Mining & Smelting Co., Ltd. Reinforced porous metal foil and process for production thereof
US9595719B2 (en) 2011-04-08 2017-03-14 Mitsui Mining & Smelting Co., Ltd. Composite metal foil and production method therefor

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* Cited by examiner, † Cited by third party
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EP1038994A1 (en) * 1998-09-14 2000-09-27 Mitsui Mining & Smelting Co., Ltd. Porous copper foil, use thereof and method for preparation thereof
KR100356404B1 (en) * 2000-03-04 2002-10-19 Nmctek Co Ltd Method and apparatus for eliminating specified hazardous substance in water using electric field
EP1566855A4 (en) * 2002-11-29 2009-06-24 Mitsui Mining & Smelting Co Negative electrode for non-aqueous electrolyte secondary cell and method for manufacture thereof, and non-aqueous electrolyte secondary cell
JP4630072B2 (en) * 2005-01-21 2011-02-09 古河電気工業株式会社 Copper foil for lithium secondary battery electrode, method for producing the copper foil, electrode for lithium secondary battery using the copper foil, and lithium secondary battery
KR101501423B1 (en) * 2013-06-18 2015-03-10 전검배 Apparatus for winding an electrolytic metal foil and Method thereof
JP6447652B2 (en) * 2017-03-28 2019-01-09 Tdk株式会社 Current collector for lithium secondary battery and lithium secondary battery
IL266910B (en) * 2019-05-27 2020-11-30 Addionics Il Ltd Electrochemically produced three-dimensional structures for battery electrodes

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EP0675213A1 (en) * 1994-03-31 1995-10-04 MITSUI MININGS & MELTING CO., LTD. Electrolytic copper foil for printed wiring boards and process for producing the same

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100365849C (en) * 2002-11-29 2008-01-30 三井金属矿业株式会社 Negative electrode for nonaqueous secondary battery, process of producing the negative electrode, and nonaqueous secondary battery
US8497026B2 (en) 2009-12-04 2013-07-30 Mitsui Mining & Smelting Co., Ltd. Porous metal foil and production method therefor
US9512527B2 (en) 2011-01-13 2016-12-06 Mitsui Mining & Smelting Co., Ltd. Reinforced porous metal foil and process for production thereof
US8980438B2 (en) 2011-04-08 2015-03-17 Mitsui Mining & Smelting Co., Ltd. Porous metal foil and production method therefor
US9595719B2 (en) 2011-04-08 2017-03-14 Mitsui Mining & Smelting Co., Ltd. Composite metal foil and production method therefor
WO2014098774A1 (en) * 2012-12-21 2014-06-26 Agency For Science, Technology And Research Porous metallic membrane
US9636639B2 (en) 2012-12-21 2017-05-02 Agency For Science, Technology And Research Porous metallic membrane

Also Published As

Publication number Publication date
JPH10195689A (en) 1998-07-28
GB9727198D0 (en) 1998-02-25

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