CA1305447C - Platinum-containing multilayer anode coating for low ph, high current density electrochemical - Google Patents

Platinum-containing multilayer anode coating for low ph, high current density electrochemical

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Publication number
CA1305447C
CA1305447C CA000518078A CA518078A CA1305447C CA 1305447 C CA1305447 C CA 1305447C CA 000518078 A CA000518078 A CA 000518078A CA 518078 A CA518078 A CA 518078A CA 1305447 C CA1305447 C CA 1305447C
Authority
CA
Canada
Prior art keywords
anode
layer
microinches
platinum
thickness
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.)
Expired - Lifetime
Application number
CA000518078A
Other languages
French (fr)
Inventor
Mark J. Geusic
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.)
BASF Catalysts LLC
Original Assignee
Engelhard Corp
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 Engelhard Corp filed Critical Engelhard Corp
Application granted granted Critical
Publication of CA1305447C publication Critical patent/CA1305447C/en
Anticipated expiration legal-status Critical
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Classifications

    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/02Electrodes; Connections thereof
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/10Electrodes, e.g. composition, counter electrode

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Chemically Coating (AREA)

Abstract

ABSTRACT
The present invention provides an anode for oxygen evolution consisting essentially of a substrate of a film forming metal having thereon a multilayer coating comprising an interior layer and an exterior layer. as follows. The interior layer con-sists essentially of substantially pore free platinum applied electrolytically to a thickness of at least about 150 microinches, then densified by heat treating in an oxygen containing atmosphere at from 600°C to 775°C so as to close the pores in the platinum layer. The exterior layer consists essentially of iridium oxide, and optionally not more than about 3% rhodium oxide. The exterior layer is applied by thermal decomposition of one or more thermally decompos-able iridium and, optionally, rhodium compounds in an oxygen contain-ing atmosphere at a temperature of not more than about 600°C.

Description

Electroformed copper foils are the backbone of modern elec-tronic devices. As integrated circuits have found their way into ever increasing numbers of products. the quantity of foil required has in-creased correspondingly yet the rate at which these foils could be pro-duced has been limited because even the best dimensionally stable anodes available were not capable Or withstanding the conditions required for optimum foil production.

SUMMARY OF THE INVENTION

In accordance with the present invention there is provided an anode for oxygen evolution consisting essentially of a substrate of a film forming metal having thereon a multilayer coating comprising an interior layer and an exterior layer, as follows. The interior layer consists essentially of substantially pore free platinum applied electro-lytically to a thickness of at least about 150 microinches, e.g.~ about 150 to 400 microinches, then densified by heat treating in an oxygen containing atmosphere at from 600C to 775C so as to close the pores in the platinum layer. The exterior layer consists essentially of iridium oxide, and optionally not more than about 3% rhodium oxide, said exterior layer having been applied by thermal decomposition of one or more thermally decomposable iridium and, optionally. rhodium compounds in an oxygen containing atmosphere at a temperature of not more than about 600C, e.g., at a temperature of from 400C to 550C, or from about 450C to about 500C.
Other aspects of the invention are described in the following detailed description.

DETAILED DESCRIPTION OF THE INVENTION AND
PREFERRED EMBODIMENTS THEREOF
__ The anodes of the present invention are particularly suitable for producing high purity, pore-free copper foils at high speed and low cost under severe conditions because these ~, ~. sp:sd ~ . , - la ~

anodes withstand high acid concentrations, current densities and temperatures which would rapidly destroy the anodes known to the prior art. In particular, the anodes of the present invention are formed by a three step process which is extremely sensitive in its details but, when carried out properly, produces extremely robust and durable anodes.
In the first step of the process, platinum is electrodeposited on a valve metal substrate which has been thoroughly descaled, degreased and cleaned. It is critical that the platinum be applied to a thickness of from at least about 150 microinches up to about 400 microinches, preferably the thickness will be at least about 225 microinches, more preferably at least about 250 microinches.
The second step of the process involves a thermal treatment referred to as "densification" which is essen-tial for obtaining the anodes of the present invention.
In the "densification" step, the platinum coated anode is heated in air and maintained at a temperature between 600 : ~:

~.

- ~ -.and 775C for about ~ to 2 hours or until the stress is relieved in the electrodeposited coating and pores resulting from the electrodeposition process have closed.
The final step in the process is applying a 5 catalytic oxide outer coating consisting essentially of at least about 97% IrO2 and up to about 3~ Rh2O3 by applying thermally decomposable iridium and rhodium compounds to the "densified" platinum coated substrate, then decomposing the compounds by heating in air to form the oxides. It has been found that it is essential to effect the decomposition at temperatures of no more than about 600C as the products formed are much less durable when higher temperatures (for example, around 690~C) are used. The amount of the thermally decomposable compounds applied should be sufficient to provide a loading of at least about 15 m /g of iridium (calculated based on the weight of the metal), preferably 20 m /g, more preferably 25 2 ~
The substrates to which the coating is applied may be any of the well known film forming metals which, if uncoated, will rapidly passivate by formation of an adherent protective oxide film in the electrolyte for which the anode is intended. Typical substrates are formed from titanium, tantalum, vanadium~ tungsten, aluminum, zirconium, niobium and molybdenum in the form of tubes, rods, sheets, meshes, expanded metals or other specialized shapes for specific applications. For formation of electrolytic copper foil, it is particularly preferred to use anodes in the shape of cylinders or as a ; 30 portion of a cylinder which conform to the shape of the mandrel or drum so that the electrolytically formed foil will be of uniform thickness and may easily be removed from the cathode drum. In many cases, the core of the anode will be copper or another highly conductive metal such as aluminum or highly conductive ferrous alloys clad with a film forming metal outer layer such as titanium.

~s~

Prior to application of the electrolytic layer, the substrate is cleaned and descaled such as by blasting with aluminum oxide particles in an air jet, then chemically cleaned and degreased. Normally, the anode is coated immediately subsequent to degreasing but the anodes may be stored for for a few days between degreasing and coating without ill effect.
The electrolytic coating of platinum may be applied by immersing the substrate in an aqueous, platinum, electroplating bath opposite a conventional dimensionally stable counterelectrode and passing a current of from about 7 to about 70 amps per s~uare foot through the substrate until at least 150, preferably 225, more preferably 250 microinches of platinum have been applied.
Any conventional platinum electroplating bath may be used. Typically, such baths are in aqueous dispersons, solutions or admixtures containing compounds of platinum such as ammine, nitrito or hydroxy complexes, as well as various known additives for brightening, improving the ductility of the deposited film and isolating impurities as well as improving the conductivity of the bath.
Typical pla-tinum compounds include H2PtCl6, KzPt(OH2~, H2Pt(NO2)2SO4 and diammine dinitroplatinum (II)~ Useful formulations for platinum electroplating baths are disclosed in F. Lowenheim, Modern Electroplating, 3rd Ed.
1974, pp. 355-357 and F. Lowenheim, Electroplating, McGraw Hill 1978~ pp.
298-299. Prepared concentrates for preparing and replenishing platinum electroplating baths are commercially available. To achieve a high quality platinum layer, the temperature of the bath should preferably be maintained at from about 150 to about 200F
(65 to 93C).
After the platinum coat has reached the desired thickness, the anode may be removed from the bath and subjected to a thermal treatment termed "densification"

, ~' `' ~,~,,...;~.. ...

:

L~ L~ 7 to stress relieve the coating and close pores therein.
If the "densification" step is omitted, or not performed properly, the anodes formed are less durable as they passivate prematurely. Thermal densification can be accomplished by heating the platinum coated anode in air, nitrogen, helium, vacuum or any convenient atmosphere to a temperature of between about 550C and 850C for from about 15 minutes to several hours depending on the nature of the as deposited platinum film. It may be determined that the thermal densification step is complete by visually observing the coating and noting when pore closure occurs and the coating becomes much more highly reflective.
After thermal densification is complete, the anode may be cooled then coated with an iridium oxide outer layer by thermal decomposition of iridium containing compounds in an oxygen containing atmosphere. Iridium compounds that may be used include hexachlororidic acid (NH4)2IrCl6 and IrC14, as well as iridium resinates and other halogen containing compounds. Typically, these compounds are dispersed in any convenient carrier such as isobutanol, and other aliphatic alcohols, then applied to the substrate by any convenient method such as dipping, brushing on or spraying. In most cases an amount of iridium bearing carrier is applied which is sufficient to deposit a loading of from about 0.5 to about 3.0 grams per square meter, preferably 1 to 2 grams per square meter, of iridium (calculated as metal) on the substrate, which is then fired in air at from about 400C to no more than about 550C, preferably 450C to about 500C, to drive off the carrier and convert the iridium compounds -to the oxides. This procedure is repeated until the total amount of iridium applied is at least about 15, preferably at least about 20, more preferably at least about 25 grams per square meter (calculated as metal).
The temperature of the thermal decomposition step is ' ~, . ., , ~

extremely critical. As will be demonstrated in the following Examples, when a decomposition temperature in excess of about 600C is used for decomposition of the iridium compounds, the resulting anode is much less durable, but when the iridium compound is decoMposed at temperatures of 600C or below, preferably from about 400C to about 550C, more preferably from 450C to 500C, the resulting anode is surprisingly durable and long lived even when evolving oxygen in baths at temperatures in excess of about 65C which will normally ruin the prior art anodes in short order.
In many cases, it will be advantageous to include up to about 3~ Rh2O3 in the iridium oxide film to promote adhesion. This may be accomplished by incorporation of any convenient, conventional rhodium compound into the iridium bearing coating composition. Rhodium resinates are particularly convenient.
Copper foils may be electroformed using the anodes of the present invention by immersing the anode in a bath at a p~ of from 0.2 to 3 containing suitable copper species such as copper sulfate, copper chloride and other soluble copper compounds opposite a cathode such as stainless steel or other corrosion resistant alloys and passing a current of from about 400 to about 2,000 amps ~ 25 per square foot of anode (4,300 to 21,000 A/m2) through ;~ the bath and evolving oxygen at the anode. It is considered particularly surprising that the anodes of the present invention exhibit high durability even when use~
at bath temperatures in excess of 65C up to about 90C.
It is also considered surprising that anodes of the present invention remain suitable for use at a sulfuric acid concentration from about 100 to about 250 grams/liter even when operating at current densities from about 500 up to about 3,000 amps per square foot (5,400 to 32,000 A/m2). Under these conditions, prior art anodes rapidly become useless and even anodes similar to : :

~ ~.

r~7 .the present invention, but not prepared strictly in accordance therewith, fail rapidly. It is extremely desirable for copper foil producers to be able to use these severe conditions as under these conditions more efficient, rapid and economical production of foil can be achieved. Thus, the anodes of the present invention satisfy a long felt but unsatisfied need for anodes which were capable of being used under conditions which are suitable for high speed, energy efficient production of high purity, pore free films of electrolytic copper foil.
They are also e~treMely suitable for those applications in which a porous foil is desired as well as for other applications involving oxygen evolution such as electrogalvanizing, electrowinning and electrosynthesis.
Example l This Example illustrates the production of an anode in accordance with the present invention. A substrate of titanium of dimensions 4" by 8" by 0.062" was descaled, cleaned and degreased, then electrolytically coated with platinum to a thickness of 250 microinches. The platinum coating was then densified by heating in air at 690C for 3/4 hour. After cooling, a coating consisting of about 98% IrO2 and 2% Rh2O3 was applied by painting the substrate with a solution of hexachloroiridic acid and a rhodium resinate dispersed in butanol, then firing in air at 450C and repeating this procedùre 15 times until the coating weight reached 15 grams of iridium ~as metal~ per square meter. When it was used in electroformir.g of copper foils at a p~ of about 0, a current density of about 1860 ASF (20,000 A/m~), and a temperature of about 60C, the anode was still operating at this writing after 4,000 hours at an essentially constant overvoltage of 2.83 volts.

~, . . .

.

Exam~ple ?
The procedure of Example 1 was repeated except that the iridium oxide (thi.rd step) was formed at 690C. When used under conditions similar to those in Example 1 (pH
0, current density 1860, and temperature of 60C) the anode failed after 620 hours.

:' , . . ~,

Claims (11)

1. An anode for oxygen evolution consisting essentially of a substrate of a film forming metal having thereon a multilayer coating comprising:
an interior layer consisting essentially of substantially pore free platinum which was applied electrolytically to a thickness of at least about 150 microinches, then densified by heat treating in an oxygen containing atmosphere at from 600°C to 775°C so as to close the pores in the platinum layer; and an exterior layer consisting essentially of iridium oxide, said exterior layer having been applied by thermal decomposition of one or more thermally decomposable iridium compounds in an oxygen containing atmosphere at a temperature of not more than about 600°C.
2. The anode of Claim 1 wherein the exterior layer further includes not more than about 3% rhodium oxide, said exterior layer having been applied by thermal decomposition of one or more thermally decomposable rhodium compounds in addition to said one or more iridium compounds.
3. The anode of Claim 1 wherein the exterior layer was formed by thermal decomposition at a temperature of from about 400°C to about 550°C.
4. The anode of Claim 1 wherein the interior layer has a thickness of at least about 225 microinches.
5. The anode of Claim 1 wherein the interior layer has a thickness of at least about 250 microinches.
6. The anode of Claim 5 wherein the exterior layer was formed by thermal decomposition at a temperature of from about 450°C to about 500°C.
7. The anode of Claim 1 wherein the interior layer has a thickness of from about 150 to about 400 microinches.
8. The anode of Claim 3 wherein the interior layer has a thickness of from about 150 to about 400 microinches.
9. The anode of Claim 6 wherein the interior layer has a thickness of from about 250 to about 400 microinches.
10. A process for electroforming of copper foil in an aqueous bath containing over 100 grams per liter of sulfuric acid, using a current density of at least about 500 amps per square foot at a temperature of over 65°C using the anode of any one of Claims 1 through 9.
11. The anode of any one of Claims 3, 4, 5, 6, 7, 8 or 9 wherein the exterior layer further includes not more than about 3% rhodium oxide, said exterior layer having been applied by thermal decomposition of one or more thermally decomposable rhodium compounds in addition to said one or more iridium compounds.
CA000518078A 1985-09-13 1986-09-12 Platinum-containing multilayer anode coating for low ph, high current density electrochemical Expired - Lifetime CA1305447C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US77591185A 1985-09-13 1985-09-13
US775,911 1985-09-13

Publications (1)

Publication Number Publication Date
CA1305447C true CA1305447C (en) 1992-07-21

Family

ID=25105919

Family Applications (1)

Application Number Title Priority Date Filing Date
CA000518078A Expired - Lifetime CA1305447C (en) 1985-09-13 1986-09-12 Platinum-containing multilayer anode coating for low ph, high current density electrochemical

Country Status (5)

Country Link
EP (1) EP0215649B1 (en)
JP (1) JPH0735597B2 (en)
AT (1) ATE60374T1 (en)
CA (1) CA1305447C (en)
DE (1) DE3677108D1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3124848B2 (en) * 1992-11-11 2001-01-15 ペルメレック電極株式会社 Manufacturing method of metal foil by electrolysis
TWI490371B (en) * 2009-07-28 2015-07-01 Industrie De Nora Spa Electrode for electrolytic applications

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4203810A (en) * 1970-03-25 1980-05-20 Imi Marston Limited Electrolytic process employing electrodes having coatings which comprise platinum
CH563464A5 (en) * 1970-09-02 1975-06-30 Engelhard Min & Chem Electrolytic anode
JPS5647597A (en) * 1979-09-25 1981-04-30 Nippon Steel Corp Insoluble electrode for electroplating and preparation thereof
GB2060701B (en) * 1979-10-12 1983-06-08 Diamond Shamrock Corp Electrode coating with platinum- group metal catalyst and semiconducting polymer
JPS56147057A (en) * 1980-04-15 1981-11-14 Ngk Spark Plug Co Ltd Production of oxygen sensor
CA1225066A (en) * 1980-08-18 1987-08-04 Jean M. Hinden Electrode with surface film of oxide of valve metal incorporating platinum group metal or oxide
US4331528A (en) * 1980-10-06 1982-05-25 Diamond Shamrock Corporation Coated metal electrode with improved barrier layer
JPS58171589A (en) * 1982-03-31 1983-10-08 Ishifuku Kinzoku Kogyo Kk Electrode for electrolysis and its manufacture
GB8316778D0 (en) * 1983-06-21 1983-07-27 Ici Plc Cathode

Also Published As

Publication number Publication date
JPS6280298A (en) 1987-04-13
JPH0735597B2 (en) 1995-04-19
EP0215649A1 (en) 1987-03-25
DE3677108D1 (en) 1991-02-28
ATE60374T1 (en) 1991-02-15
EP0215649B1 (en) 1991-01-23

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