US3087870A - Process for plating adherent lead dioxide - Google Patents

Process for plating adherent lead dioxide Download PDF

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Publication number
US3087870A
US3087870A US822715A US82271559A US3087870A US 3087870 A US3087870 A US 3087870A US 822715 A US822715 A US 822715A US 82271559 A US82271559 A US 82271559A US 3087870 A US3087870 A US 3087870A
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metal
lead dioxide
lead
plating
bath
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US822715A
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Herman M Zimmerman
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Union Carbide Corp
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Union Carbide Corp
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C25D9/06—Electrolytic coating other than with metals with inorganic materials by anodic processes
    • 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
    • H01M4/14—Electrodes for lead-acid accumulators
    • H01M4/16—Processes of manufacture
    • 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

  • lead dioxide was deposited anodically from aqueous acid solutions of lead nitrate onto base metals such as nickel, stainless steel, terneplate and platinum.
  • base metals such as nickel, stainless steel, terneplate and platinum.
  • the conditions for maximum adherence were unknown, however, and when a plated strip was blanked out in a punch press, the lead dioxide chipped or cracked unpredictably.
  • the main object of this invention is to provide a process for securely depositing lead dioxide onto a base metal.
  • Another object of the invention is to provide a novel process for making lead dioxide positive electrodes.
  • the process in accordance with the present invention and whereby the foregoing objects are attained comprises plating under conditions wherein the base metal, preferably nickel, is actively dissolved anodically, is then suddenly passivated and shifted over to lead dioxide deposition by momentarily applying a greater anode potential or :by lifting the metal strip while still electrically con nected almost entirely from the electrolysis bath, and then slowly replating, after which lead dioxide deposition is continued at a reduced current density.
  • the base metal preferably nickel
  • a modification of this process giving an equivalent product and being more readily susceptible to chemical control and maintenance comprises subjecting a chemically clean and acid-etched nickel or nickel-plated surface to a passivation treatment consisting of a cathodic step and an anodic step in a dilute nitric acid bath followed by the plating of lead dioxide on the metal from nearly neutral lead nitrate solution.
  • the base metal was nickel-clad steel. It was electrolytically cleaned in a proprietary alkaline bath and thoroughly rinsed. It was then anodically etched at about 25 amperes per square foot (a.s.f.) for about fifteen seconds in three percent hydrochloric acid and thoroughly rinsed. The following passivation treatment was performed in a three percent nitric acid bath. The cleaned and etched sample was soaked for about eight seconds, during which time it was made cathodic at about 20 a.s.f. if desired.
  • the cathodic phase of the passivation can be omitted.
  • the cathodic portion of the passivation is employed as insurance against deleterious oxide films previously formed.
  • a process for electrolytically depositing lead dioxide on a base metal comprising anodically dissolving a porn'on of said metal, passivating said metal in a dilute nitric acid bath by making said metal cathodic and then anodic, placing said metal in a warm, almost neutral lead nitrate bath, and plating lead dioxide anodically onto said metal using a low current density.
  • a process for electrolytically depositing lead dioxide on a base metal comprising electrolytically cleaning said metal in an alkaline bath, rinsing said cleaned metal, anodically etching said metal in a dilute hydrochloric acid bath, rinsing said metal, passivating said metal in a dilute nitric acid bath, by making said metal cathodic and then anodic, transferring said metal to a nearly neutral Warm lead nitrate bath, and plating lead dioxide anodically onto said metal using a low current density against lead cathodes.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Electroplating Methods And Accessories (AREA)

Description

United States Patent 3,087,870 PROCESS FOR PLATHNG ADHERENT LEAD DEOXHDE Herman M. Zimmerman, Lakewood, Ohio, assignor to Union Carbide Corporation, a corporation of New York No Drawing. Filed June 22, 1959, Ser. No. 822,715 6 Claims. (Cl. 204--32) This invention relates to a process for plating adherent lead dioxide depolarizers on thin metal strips intended for use as the positive electrode in reserve-type batteries characterized by a high flash current and eificient perform ance at low temperatures.
Heretofore lead dioxide was deposited anodically from aqueous acid solutions of lead nitrate onto base metals such as nickel, stainless steel, terneplate and platinum. The conditions for maximum adherence were unknown, however, and when a plated strip was blanked out in a punch press, the lead dioxide chipped or cracked unpredictably.
The main object of this invention is to provide a process for securely depositing lead dioxide onto a base metal.
Another object of the invention is to provide a novel process for making lead dioxide positive electrodes.
The process in accordance with the present invention and whereby the foregoing objects are attained comprises plating under conditions wherein the base metal, preferably nickel, is actively dissolved anodically, is then suddenly passivated and shifted over to lead dioxide deposition by momentarily applying a greater anode potential or :by lifting the metal strip while still electrically con nected almost entirely from the electrolysis bath, and then slowly replating, after which lead dioxide deposition is continued at a reduced current density.
A modification of this process giving an equivalent product and being more readily susceptible to chemical control and maintenance comprises subjecting a chemically clean and acid-etched nickel or nickel-plated surface to a passivation treatment consisting of a cathodic step and an anodic step in a dilute nitric acid bath followed by the plating of lead dioxide on the metal from nearly neutral lead nitrate solution.
As an example of the practice of the invention, the following typical specification is given:
The base metal was nickel-clad steel. It was electrolytically cleaned in a proprietary alkaline bath and thoroughly rinsed. It was then anodically etched at about 25 amperes per square foot (a.s.f.) for about fifteen seconds in three percent hydrochloric acid and thoroughly rinsed. The following passivation treatment was performed in a three percent nitric acid bath. The cleaned and etched sample was soaked for about eight seconds, during which time it was made cathodic at about 20 a.s.f. if desired.
It was then made anodic at about 80 a.s.f. for about twelve seconds with copious evolution of oxygen from the surface. Anodic treatment was continued for 28 more seconds at 20 a.s.f. The passivated sample Was transferred to a nearly neutral lead nitrate bath (specific gravity 1.300, pH 4.0, temperature 50 C.) and lead 3,087,870 Patented Apr. 30, 1963 dioxide plated anodically at 35 a.s.f. to the thickness desired. Lead cathodes were employed. Additions of lead oxide (PbO) serve to maintain proper pH in this tank.
Relative to the passivation step it has been found that on continuous plating lines, particularly, the cathodic phase of the passivation can be omitted. In batch operations and particularly if for any reason the etch step is omitted, the cathodic portion of the passivation is employed as insurance against deleterious oxide films previously formed.
What is claimed is:
1. A process for electrolytically depositing lead dioxide on a base metal comprising anodically dissolving a porn'on of said metal, passivating said metal in a dilute nitric acid bath by making said metal cathodic and then anodic, placing said metal in a warm, almost neutral lead nitrate bath, and plating lead dioxide anodically onto said metal using a low current density.
2. The process of claim 1 wherein said base metal is nickel-clad steel.
3. A process for electrolytically depositing lead dioxide on a base metal comprising electrolytically cleaning said metal in an alkaline bath, rinsing said cleaned metal, anodically etching said metal in a dilute hydrochloric acid bath, rinsing said metal, passivating said metal in a dilute nitric acid bath, by making said metal cathodic and then anodic, transferring said metal to a nearly neutral Warm lead nitrate bath, and plating lead dioxide anodically onto said metal using a low current density against lead cathodes.
4. The process of claim 3, wherein said base metal is made cathodic for about eight seconds at about 20 amperes per square foot.
5. The process of claim 3 wherein said metal is made anodic for about twelve seconds at about amperes per square foot.
6. The process of claim 3, wherein said nitrate solution has a specific gravity of 1.300 and a pH of 4.
References Cited in the file of this patent UNITED STATES PATENTS 2,571,616 Ruben Oct. 16, 1951 2,711,496 Ruben June 21, 1955 2,846,378 Hoifman Aug. 5, 1958 2,851,405 Dyman et a1. Sept. 9, 1958 2,872,405 Miller et al. Feb. 3, 1959 2,915,444 Meyer Dec. 1, 1959 2,945,790 Grigger July 19, 1960 3,002,900 Henry et a1. Oct. 3, 1961 FOREIGN PATENTS 611,577 Great Britain Nov. 1, 1958 OTHER REFERENCES The Metal Industry (Haas et al.), volume 23, No. 11, November 1925, pages 451 and 452.
Plating (Brune et 211.), September 1955, pages 1127 and 1128.

Claims (1)

1. A PROCESS FOR ELECTROLYTICALLY DEPOSITING LEAD DIOXIDE ON A BASE METAL COMPRISING ANDICALLY DISSOLVING A PORTION OF SAID METAL, PASSIVATING SAID METAL IN A DILUTE NITRIC ACID BATH BY MAKING SAID METAL CATHODIC AND THEN ANODIC, PLACING SAID METAL IN A WARM, ALMOST NEUTRAL LEAD NITRATE BATH, AND PLATING LEAD DIOXIDE ANODICALLY ONTO SAID METAL USING A LOW CURRENT DENSITY.
US822715A 1959-06-22 1959-06-22 Process for plating adherent lead dioxide Expired - Lifetime US3087870A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3819414A (en) * 1972-10-02 1974-06-25 Gen Electric Storage battery and positive electrode therefor
FR2682817A1 (en) * 1991-10-22 1993-04-23 Gorodskoi Studenchesko Molodez Method of manufacture of an electrode for a lead accumulator and lead accumulator comprising such an electrode

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB611577A (en) *
US2571616A (en) * 1951-04-06 1951-10-16 Ruben Samuel Electric current producing cell
US2711496A (en) * 1952-09-27 1955-06-21 Ruben Samuel Lead peroxide rectifiers and method of making the same
US2846378A (en) * 1956-02-07 1958-08-05 American Potash & Chem Corp Electrode and its manufacture
US2851405A (en) * 1953-07-03 1958-09-09 Sylvania Electric Prod Titanate rectifiers
US2872405A (en) * 1955-12-14 1959-02-03 Pennsalt Chemicals Corp Lead dioxide electrode
US2915444A (en) * 1955-12-09 1959-12-01 Enthone Process for cleaning and plating ferrous metals
US2945790A (en) * 1955-12-14 1960-07-19 Pennsalt Chemicals Corp Method of electroplating lead dioxide
US3002900A (en) * 1949-10-07 1961-10-03 James W Henry Preparation of plates for deferred action type batteries

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB611577A (en) *
US3002900A (en) * 1949-10-07 1961-10-03 James W Henry Preparation of plates for deferred action type batteries
US2571616A (en) * 1951-04-06 1951-10-16 Ruben Samuel Electric current producing cell
US2711496A (en) * 1952-09-27 1955-06-21 Ruben Samuel Lead peroxide rectifiers and method of making the same
US2851405A (en) * 1953-07-03 1958-09-09 Sylvania Electric Prod Titanate rectifiers
US2915444A (en) * 1955-12-09 1959-12-01 Enthone Process for cleaning and plating ferrous metals
US2872405A (en) * 1955-12-14 1959-02-03 Pennsalt Chemicals Corp Lead dioxide electrode
US2945790A (en) * 1955-12-14 1960-07-19 Pennsalt Chemicals Corp Method of electroplating lead dioxide
US2846378A (en) * 1956-02-07 1958-08-05 American Potash & Chem Corp Electrode and its manufacture

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3819414A (en) * 1972-10-02 1974-06-25 Gen Electric Storage battery and positive electrode therefor
FR2682817A1 (en) * 1991-10-22 1993-04-23 Gorodskoi Studenchesko Molodez Method of manufacture of an electrode for a lead accumulator and lead accumulator comprising such an electrode

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