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Degradation Characteristics of Air Cathode in Zinc
Degradation Characteristics of Air Cathode in Zinc
each side of the battery top were fifteen knife switches the dendrite which as a counsequence heated up, and
which were ganged together with a Lucite strip so that finally melted. The electronic path was thus opened, and
they could be operated simultaneously. The knife the cell potential increased again. The current, of course,
switches on one side of the battery top served to connect decreased to its original value. The dendrite then started
the anode of one cell to the cathode of the next cell to grow again, and the whole process was repeated. In
throughout the whole battery stack. On the other side time as more dendrites were formed, the pattern of the
of the battery top, the knife switches served to connect potential oscillations changed, and finally the potential
the anode of one cell to the third electrodes of the next dropped to a low value from which it never increased
cell throughout the whole battery stack. In the discharge again.
mode the anode-cathode switches were closed while The cycle life and failure mode of several single cells
the anode-third electrode switches were opened. In the is shown in Table 1. Six of these cells, No. l-5a. had
charge mode the anode-cathode switches were opened, one layer of Permion 300 separator between the anode
while the anode-third electrode switches were closed. and the third electrodes. The first three cells, No. 1-3,
Terminal posts were mounted at the ends of the battery had one layer of Dyne1 separator between the third
for connecting a load and a battery charger. electrodes and the air cathodes. In the other cells the
The single cells and battery were tested by determining Dyne1 was replaced by one layer of polypropylene separa-
the cycle life under a variety of conditions. This was done tor. This was because the Dyne1 separator was thin and
by using a simple discharge circuit consisting of a carbon therefore hard to work with, and in addition it had a
pile rheostat and an ammeter, and a charging circuit tendency to melt at high rates of discharge. The poly-
consisting of a battery charger with a suitable output propylene separator did not have these disadvantages.
voltage and an ammeter. All of the work reported here Cells 5 and 5a had the same cathode assembly but differ-
was carried out at ambient temperatures. ent anode-third electrode packages. When cell 5 failed,
the anode-third electrode package was removed, and the
cathode assembly was washed with hot water, distilled
water, boric acid solution for 16 hr, and finally with
Results and Discussion distilled water. After drying, a new anode-third electrode
The cycling procedure used to test the single cells assembly was inserted.
consisted of discharge at currents up to 15 A followed Of the first six cells tested, No. 5 survived for 74
by charge at currents up to 3 A. A low charging rate was cycles, No. 5a for 4+ cycles, and No. 4 for 34 cycles.
used to minimize the growth of zinc dendrites. The cells That cell No. 5a had an appreciable cycle life was indeed
were cycled until they failed. One mode of failure that surprising since it was charged at currents up to 6 A.
was ultimately expected was the formation of internal The cycle life of the first three cells was very low. With
shorts resulting from the penetration of the separator the exception of the first cell, the failure mode was a short
by zinc dendrites. Such a mode of failure was indicated between the anode and the third electrode. These shorts,
by (a) poor charge acceptance; (b) the anode and third which were barely visible to the naked eye, occurred
electrode exhibiting the same potential at open circuit through the separator, at the edges where the separator
vs. a mercury-mercuric oxide reference electrode; and was heat sealed, or over the top of the separator. The
(c) potential oscillations in the cell potential-time trace poor reproducibility of the performance of the first six
during charge. cells is hard to explain. It is possible that differences in
A typical cell potential-time trace exhibiting oscilla- the mode of construction, or a non-uniformity of the
tions is shown in Fig. 3. These potential oscillations Permion separator could be responsible. Cells No. 6 and
resulted from the alternate formation and removal of 7 each had three layers of Permion separator between the
zinc dendrites. When a zinc dendrite touched the third anode and third electrodes. The cycle life of these cells,
electrode, a low resistance electronic path was produced. however, was disappointingly and unaccountably low.
The cell potential dropped and the current correspond- One of these cells failed because of a short between
ingly increased. All of the current tended to flow through the cathode and the third electrode, and the other failed
1 1 layer Dyne1 1 layer Permin 300 Cell dried out on standing after
first discharge
2 1 layer Dyne1 1 layer Permion 300 Anode shorted to third electrode
3 1 layer Dyne1 1 layer Permion 300 Anode shorted to third electrode
4 1 layer Polypropylene 1 layer Permion 300 Anode shorted to third electrode
5 1 layer Polypropylene 1 layer Permion 300 Anode shorted to third electrode
5a 1 layer Polypropylene 1 layer Permion 300 Anode shorted to third electrode
6 1 layer Polypropylene 3 layers Permion 300 Third electrode shorted to cathode
7 1 layer Polypropylene 3 layers Permion 300 Anode shorted to third electrode
8 1 layer Polypropylene 4 layers of fibrous Anode shorted to third electrode
sausage casing
Fig. 1. Secondary zinc-air cell.
[facing p. 46
Fig. 2. Cutaway view of secondary zinc-air cell.
3 IN.
4 *
because of a short between the anode and the third and at 60 A it was O-7 V. In all about 40 A-hr or half of
electrode. The best performance was exhibited by cell the capacity of the anode, was utilized.
No. 8 which contained four layers of fibrous sausage Often in the operation of fuel cell air cathodes in a
casing between the anode and the third electrodes. This potassium hydroxide electrolyte, three problems are
cell survived for 16; cycles after which it failed because encountered [6]. They are (a) “weeping”, i.e. the passage
of a short between the anode and the third electrodes. of electrolyte through the electrode structure to form
The Permion 300 separator showed no evidence of droplets on the gas phase side of the electrode; (b)
degradation as a result of coming into contact with flooding of the active layer; and (c) carbonate precipation
oxygen that was evolved at the third electrode during within the pores of the electrode. All of these effects can
charge. The fibrous sausage casing, however, particularly lead to a decrease in the performance of an air electrode.
the outer layers, was embrittled as a result of contact In the work reported here, none of these problems were
with oxygen. encountered.
The open-circuit cell potentials were 1.3-l-4 V. On During the operation of the cells the electrolyte level
discharge the potential dropped to 1*0-1-l V at a current was observed to decrease. While some of this loss was
drain of 10 A, while on charge the potential (anode vs. caused by evaporation and sputtering from the top of the
third electrode) was 2.2-2-5 V at a current of 2 A. After cells, it is believed that a substantial loss occurred by
several cycles the cell potential on discharge dropped to transpiration of water vapor through the air cathodes.
0.7-09 V. This was due to an increase in the polarization The loss of water from the cells led to a decrease in the
of the zinc electrode. cell potential during discharge, and an increase in the
The capacity of the zinc anodes initially was 84 A-hr. potential (anode vs. third electrode) during charge.
In the first cycle about half of this capacity was used up. Another possible consequence of the loss of water from
As the cells were cycled the useful capacity that could the cells during charge was the promotion of shape change
be obtained was observed to decrease. In cell No. 5 the at the anodes leading to a premature loss of capacity.
capacity was 30 A-hr in the fourth cycle, while it was The power curve for the fifteen-cell battery is shown in
only 18 A-hr in the seventh cycle. A cutoff voltage of Fig. 5. The peak power was 366 W at a current drain of
O-7 V was used. This decrease in capacity with cycling 38 A. The corresponding battery voltage was 9.6 V. At
is not a new phenomenon as it has often been observed open circuit the battery voltage was 21.1 V. Up to the
in the development of silver-zinc batteries [4]. A possible maximum power the battery voltage rapidly reached a
explanation is shape change, i.e. a redistribution of steady value for a particular current. However, beyond
zinc which occurs on the anode support with repeated the maximum power, steady voltage readings could not
cycling [5]. be obtained. Because of this the descending limb of the
An attempt was made to determine the limiting current power curve is probably in error.
of the zinc anodes on discharge. For this purpose the The weight of the battery was 20 lb dry, and 24 lb wet.
cathode assembly from cell No. 5a was used after washing The fifteen cells weighed 12$ lb, while the case and
in the manner described previously. A zincanode wrapped some of the switching hardware weighed 7s lb. The
in polypropylene separator was inserted into this cathode volume of the battery was 0.4 ft3. Combining these data
assembly. The third electrodes were omitted for this with the power data shown in Fig. 5 and the capacity
investigation. The cell was discharged initially at 25 A data reported above gives the energy and peak power
for 30 min. During this period the cell potential was densities shown in Table 2. For comparison, the energy
1.0 V. The current was then increased to 45 A for 30 min. and peak power densities of a mechanically rechargeable
The cell potential fell immediately to 0.93 V and then 20~11 zinc-air battery [7] and of the lead-acid battery
slowly dropped to 0.87 V. At this point the current was [8] are also included in Table 2. It will be seen that the
increased again. At 50 A the cell potential was 0.85 V, peak power density of the electrically rechargeable
I I TIME (MIN) -
Discharge Charge
~_------h__.-, ---_-7
----
During the cycling of the battery, the capacity was There was no evidence during the cycling of the battery
observed to decrease from cycle to cycle. Initially, it was of shorts between the anode and the third electrodes,
about 40 A-hr, but was only 10 A-hr in the fifth cycle. or between the third electrodes and the cathode. Battery
Similar behavior was observed in the single cell studies. failure, apparently, was caused solely by the loss in
In the tith cycle, on discharge, three cells reversed. After capacity of the zinc anodes.
charging the battery these cells were replaced. Again the
battery was cycled. In the sixth discharge the capacity
Acknowledgements-The authors wish to thank Marion E. Wheatley
obtained was 15 A-hr, and in the seventh cycle it was and Richard L. Adams of the Electrochemistry Department,
10 A-hr. During discharge in the seventh cycle three Research Laboratories, General Motors Corporation, for their
more cells reversed. These cells were replaced after assistance in this work.
charging. In the eighth and ninth cycles four more cells
reversed on discharge.
The cell reversal was completely unexpected. It occurr-
ed, apparently, because of a nonuniform decrease in the
capacity of the anodes from cycle to cycle. When an
anode lost its useful capacity the potential increased to
rhe point where oxygen was evolved. At this point the
anode was positive to the air cathode which was still References
functioning normally. This is illustrated by the following [l] R. R. Witherspoon, Paper presented at S.A.E. Congress,
data: Detroit, Mich., U.S.A., Paper No. 690204, 16 January (1969).
Potential (V) 121 R. Thacker. Electrochimica Acta. 14. 433 (19691.
r-----7 [3j R. S. Gum&io, U.S. Patent 3,21$,48ti, 23 November (1965).
Cell Cathode Anode [4] T. P. Dirkse, ASTIA Rpt. AD 804559, January (1967).
Potential VS. VS. [5] G. A. DaIin, Paper presented at the Fall Meeting of the Electro-
Zn Reference Zn Reference chemical Society, October, 1968, Extended Abstracts of Battery
WI
Division, 13, Abst. No. 299.
C ell behaving normally 1.06 1.25 0.20 [6] K. R. Williams (Editor) .4n Introduction to Fuel Cells, Elsevier,
(Discharge at 10 A) New York (1966).
Same cell after reversal -1.10 1.17 2.25 [7] R. R. Witherspoon, private communication.
! Discharge at 10 A) [S] J. J. Lander, private communication.