An electrochemical study of lead acid battery positive electrodes

213 Pages·2017·3.8 MB·English

Loughborough University
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An electrochemical study of
lead acid battery positive
electrodes
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the award of Doctor of Philosophy of Loughborough University.
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Publisher: (cid:13)c Simon Webster
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LOUGHBOROUGH
UNIVERSITY OF TECHNOLOGY·
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AN ELECTROCHEMICAL STUDY
OF
LEAD ACID BATTERY
POSITIVE ELECTRODES
by
SIMON WEBSTER
Supervisor: Professor N. A. Hampson
A Doctoral thesis submitted in
partial fulfilment of the requirement
for the award of Doctor of
Philosophy of the Loughborough
University of Technology,
September 1986
'.

The work described in this thesis has not been submitted, in full
or in part, to this or any other institution for a higher degree .
..
~
The thesis describes an electrochemical investigation into the
properties of various lead alloys used in the manufacture of lead
acid battery positive electrodes. The electrochemical results have
been discussed in terms of current nucleation and growth theories.
The morphological aspects of the discharge reaction have been
investigated and theories are presented describing some of the
important influences of various alloying ingredients. It has been
found possible to suggest trends important in the optimisation of
alloy composition for modern lead-acid battery grids. This aspect
is especially relevant to the development of maintenance free
technology.
ACKNOWLEDGEMENTS
I wish to thank Professor Noel Hampson for his supervision and
encouragement over the last three years.
I am also grateful to all the members of the electrochemistry group
for their friendship. I wish to thank in particular Dr. P.J. Mitchell
for his advice and 'useful discussions' on electrocrystallisation
theory.
I would also like to thank Mr. J.1. Dyson for his personal interest
in the project and financial support is acknowledged from Oldham
Batteries Ltd. and S.E.R.C.
My thanks go to Miss A. Hurst for typing this thesis and also to
members of the department's technical staff for assistance during the
project.
Finally I would like to thank my wife Catherine for the support
she has given me throughout this study and especially for her patience
during the thesis 'write-up' period.
CONTENTS
CHAPTER PAGE
1. Introduction 1
2. Theoretical Principles 8
3. The Theory of the Experimental 26
4. Experimental Techniques 48
5. The Electrochemical Properties of Solid Lead After
Alloying with Calcium, Tin and Antimony 54
6. Morphology of Planar Lead Dioxide Electrodes After
Continued Potentiodynamic Cycling 74
7. The Corrosion of Various Lead Alloys in 5M H2S04 79
8. The Electrochemical Properties of Solid Lead-Bismuth
Alloys in 5M H2S04 87
9. The Electroreduction Processes of Planar and Porous Lead
Dioxide on Various Lead Alloy Supports 97
10. Final Discussions 111
References 114
Appendix 124