The electrochemistry of planar and porous lead dioxide electrodes
has been investigated using the techniques: linear sweep voltammetry,
potentiostatic pulse experiments and Faradaic (a.c.) impedance studies.
The first two techniques were digitally controlled and the data were
acquired at high speed and could be easily retrieved after storage. A
morphological examination on the electrodes was also carried out using
scanning electron microscopy.
The electrochemical behaviour of flat lead in sulphuric acid at
concentrations in excess of 5 mol dm-3 has been studied. Various solid
lead alloys in different sulphuric acid concentrations were investigated
together with porous PbO2 on different lead alloy supports. It was
found that the acid concentration had a marked effect on the electrochemistry
of the electrodes. The current transients obtained from
potentiostatic step experiments with the porous PbO2 electrodes were
nearly all of a complex nature and some attempt was made to match the
data with established mathematical relationships for electracrystallisation
processes. The alloys used were of industrial importance and they were
lead-antimonyp lead-tin-calcium and lead-tin-bismuth-calcium. Also
various automotive positive pastes were employed to form the porous PbO2
A.C. impedance studies were carried out on the porous PbO2 electrodes.
An analogue was found which described the discharge process of Pb02.
Doctoral Thesis. Submitted in partial fulfilment of the requirements for the award of Doctor of Philosophy of Loughborough University.