The effect of bismuth on the lead acid battery system

255 Pages·2017·11.02 MB·English

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The effect of bismuth on the
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LOUGHBOROUGH
UNIVERSITY OF TECHNOLOGY,
. LIBRARY
AUTHOR/FILING TITLE
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THE EFFECT OF BISMUTH ON THE
LEAD-ACID BATTERY SYSTEM
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Mark Johnson
A Doctoral thesis suhnitted in partial fulfilment of the requirements
for the award of Doctor of Philosphy of Loughborough University of
Technology •
January 1988
. by Mark Johnson

The Work in this thesis has not been sutmitted, in full or in part, to
this or any other institution for a higher degree •
•
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I thank my supervisors Prof. N.A. Harnpson and Dr. S.R. Ellis for
guiding me through this topic. I am particularly grateful to Steve Ellis
for his enoouragement during the periods when things were frustrating
and for the considerable amount of his time which he spent in
introducing me to the methods of electrochemistry. My gratitude is also
extended to Dr. ~ Ollpin, from Chloride Technical Ltd., for his
interest and guidance and to Australian Associated Smelters pty Ltd.,
, .
for their financial support.
To my fellow research students, with whcxn it has mostly been a
pleasure to work, go my thanks and best wishes for the future. I would
also like to thank the Chemistry Dept. technical staff for provision of
various pieces of laboratory equipment.
Finally, my appreciation extends to the staff and students
involved with the Chaplaincy, who have been very supportive.
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SUMMARY
The effect of bismuth on the electrochemisb:y of the lead-acid
battery has been investigated using the techniques of linear sweep
voltanrneb:y, chronocoul<imetric and galvanostatic cycling, potentiostatic
pulse experiments and corrosion measurements. Optical and scaru;ling
electron microscopy enabled a morphological examination of the
electrodes to be =ied out. The concentration of bismuth range:1 fron 5
x 10-4 to 4.91 wt%. The effect of the presence of Bi was evaluated on
both the neagtive and positive p1a~es. On the negative, investigations
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were carried out into the hydrog~ evolution reaction and on the effect
of bismuth on the grcmt.h and develo]7llent of the lead/lead sulphate
active material. Research into aspects of positive plate performance
have covered corrosion, oxygen evolution, pasted plates,
electrocrystallisation and cycling of grid wires.
The effect of bismuth in increasing the hydrogen evolution
overpotential and improving the nucleation of lead sulphate were noted
on the negative plate. On the positive, bismuth had a generally
deleterious effect, it increases the lead dioxide crystallisation
overpotential, facilitates oxygen evolution, increases sulphation and
leaches fron the electrode. The advantages of bismuth on the positive
are confined to improving the corrosion layer by making it more canpact
and, at low levels, improving the porosity and thus the utilization, of
the pasted plates.
Thus it is recxmnended that bismuth be kept below 0.05% in the
positive, but be allowed up to 1% in the negative.
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CXlNTENTS
Chapter 1 Introduction 1
Chapter 2 Thoeretical Principles . 9
Chapter 3 Theories of Relevant Electrochemical 31
. Techniques
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Chapter 4 Experimental Techniques 49
Chapter 5 The Effect of Bismuth on the Microstructure 57
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of Lead
Chapter 6 Hydrogen Evolution on Lead and Lead-Bismuth 61
Alloys
Chapter 7 Positive Cycled Planar Lead and Lead-Bismuth 68
Electrodes
Chapter 8 The Effect of Bismuth Oxide on Pasted Positive 79
Plate Perfo:cnance
Chapter 9 Lead to Lead Sulphate Cycling of Planar Lead 89
and Alloy Electrodes
Chapter 10 Electrocrystallisation 98
Chapter 11 Corrosion of Lead and Lead-Bismuth Alloys 121
Chapter 12 Final Discussion 134
References 138
Appendix 1 149
Appendix 2 150