Skip to main content Accessibility help

In situ XRD investigation of the evolution of surface layers on Pb-alloy anodes

  • Marie Clancy (a1), Mark J. Styles (a2), Colleen J. Bettles (a1), Nick Birbilis (a1), Justin A. Kimpton (a3) and Nathan A. S. Webster (a4)...


The electrochemical behaviour of a number of Pb-based anode alloys, under simulated electrowinning conditions, in a 1.6 M H2SO4 electrolyte at 45 °C was studied. Namely, the evolution of PbO2 and PbSO4 surface layers was investigated by quantitative in situ synchrotron X-ray diffraction (S-XRD) and subsequent Rietveld-based quantitative phase analysis (QPA). In the context of seeking new anode alloys, this research shows that the industry standard Pb-0.08Ca-1.52Sn (wt%) anode, when exposed to a galvanostatic current and intermittent power interruptions, exhibited poor electrochemical performance relative to select custom Pb-based binary alloys; Pb–0.73Mg, Pb–5.05Ag, Pb–0.07Rh, and Pb–1.4Zn (wt%). The in situ S-XRD measurements and subsequent QPA indicated that this was linked to a lower proportion of β-PbO2, relative to PbSO4, on the Pb-0.08Ca-1.52Sn alloy at all stages of the electrochemical cycling. The best performing alloy, in terms of minimisation of overpotential during normal electrowinning operation and minimising the deleterious effects of repeated power interruptions – both of which are significant factors in energy consumption – was determined to be Pb–0.07Rh.


Corresponding author

a) Author to whom correspondence should be addressed. Electronic mail:


Hide All
Bruker (2014). TOPAS, version 5. Bruker AXS Inc., Madison, Wisconsin, USA.
Butler, G. and Copp, J. L. (1956). “The thermal decomposition of lead dioxide in air,” J. Chem. Soc. 725735.
Camurri, C. P., López, M. J., Pagliero, A. N., and Vergara, F. G. (2001). “Deformations in lead–calcium–tin anodes for copper electrowinning,” Mater. Charact. 47, 105109.
Clancy, M., Styles, M. J., Bettles, C. J., Birbilis, N., Chen, M., Zhang, Y., Gu, Q., Kimpton, J. A., and Webster, N. A. S. (2015). “ In situ synchrotron X-ray diffraction investigation of the evolution of a PbO2/PbSO4 surface layer on a copper electrowinning Pb anode in a novel electrochemical flow cell,” J. Synchrotron Radiat. 22, 366375.
Cullity, B. D. (1978). Elements of X-ray Diffraction, 2nd ed. (Addison-Wesley, Reading), pp. 132135.
D'Antonio, P. and Santoro, A. (1980). “Powder neutron diffraction study of chemically prepared β-lead dioxide,” Acta Crystallogr. B36, 23942397.
Goodwin, T. H. and Whetstone, J. (1947). “The crystal structure of ammonium nitrate III, and atomic scattering factors in ionic crystals,” J. Chem. Soc. 14551461.
Hill, R. J. and Howard, C. J. (1987). “Quantitative phase analysis from neutron powder diffraction data using the Rietveld method,” J. Appl. Crystallogr. 20, 467474.
Pavlov, D. (2011). Lead-Acid Batteries: Science and Technology (Elsevier, Amsterdam).
Pavlov, D. and Monahov, B. (1996). “Mechanism of the elementary electrochemical processes taking place during oxygen evolution on the lead dioxide electrode,” J. Electrochem. Soc. 143, 36163629.
Rowles, M. R. (2010). “CONVAS2: a program for the merging of diffraction data,” Powder Diffr. 25, 297301.
Schlesinger, M., King, M., Sole, K., and Davenport, W. (2011). Extractive Metallurgy of Copper, 5th ed. (Elsevier, Amsterdam).
Shannon, R. D. (1976). “Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides,” Acta Crystallogr. A32, 751767.
Straumanis, M. E. (1949). “The precision determination of lattice constants by the powder and rotating crystal methods and applications,” J. Appl. Phys., 20, 726734.
Wyckoff, R. W. G. (1963). Crystal Structures (John Wiley Interscience Publishers, New York), Vol. 1, pp. 239444.



Full text views

Total number of HTML views: 0
Total number of PDF views: 0 *
Loading metrics...

Abstract views

Total abstract views: 0 *
Loading metrics...

* Views captured on Cambridge Core between <date>. This data will be updated every 24 hours.

Usage data cannot currently be displayed