Doctoral Dissertations


"The recovery of lead from scrap batteries using hydrometallurigical techniques requires a chemically stable and electrochemically attractive anode in the electrowinning step. A high reaction rate of oxygen evolution and a low generation of lead dioxide are necessary to ensure a satisfactory efficiency. One way to inhibit the formation of lead dioxide is by employing additives, such as phosphorus or arsenic, in the electrolyte. The objective of this research was to produce and electrochemically characterize lead dioxide electrodes and study the effect of the different additives on the anodic reactions.

Lead dioxide was plated on both graphite and titanium substrates using a nitrate solution. The deposits consisted primarily of β-Pb02 along with lesser amounts of α-Pb02 . The morphology of various lead dioxide coatings was dependent on the plating solution.

Phosphorus and arsenic additions to a lead fluosilicate solution prevented the formation of lead dioxide while dramatically polarizing the overall anodic reactions. The cobalt additive catalyzed the oxygen evolution on lead dioxide. Phosphorus and arsenic were adsorbed in the lead dioxide electrode and modified the crystal growth and morphology. Electrochemical impedance spectroscopy tests revealed that the inhibition of the anodic reactions was related to the phosphorus and arsenic concentration. The adsorption of phosphorus or arsenic ions at the electrode during lead dioxide formation increased the charge transfer resistance for lead dioxide formation and polarized lead dioxide crystallization to overpotentials where the oxygen evolution reaction is dominant making lead electrowinning effective and efficient"--Abstract p. iv


Thomas J. O'Keefe

Committee Member(s)

Donald R. Askeland
Ronald A. Kohser
David G. C. Robertson
James W. Johnson, 1930-2002


Materials Science and Engineering

Degree Name

Ph. D. in Metallurgical Engineering


The financial support by Kansas State University EPA through grant KSU project 90-16 to this study is gratefully acknowledged.


University of Missouri--Rolla

Publication Date

Summer 1994

Journal article titles appearing in thesis/dissertation

  • Evaluation of electrodeposited lead dioxide
  • Electrodeposition of lead dioxide from nitrate and other media
  • Effect of cobalt, phosphorus and arsenic additives on lead dioxide anodes in lead electrowinning


xvi, 136 pages

Note about bibliography

Includes bibliographical references (pages 12, 33 and 77)


© 1994 Christel M. A. Bemelmans, All rights reserved.

Document Type

Dissertation - Restricted Access

File Type




Thesis Number

T 6806

Print OCLC #


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