4-2 zy
zyxwvu
Water loss in valve regulated batteries
Chalasani S C Bose
Power Systems, Lucent Technologies,
3000 Skyline Drive, Mesquite, TX 75 149
Abstract: Water loss in a Valve Regulated Lead
Acid battery (VRLA) due to inefficient oxygen
recombination, corrosion of the positive grid, and
water permeation through the battery housing
were measured as a function of the electrolyte
condition from a flooded state to a starved state.
In starved electrolyte condition, the rate of
measured water loss was found to be consistent
with prediction based on weight loss. However, in
flooded electrolyte conditions the rate of water
loss determined by weight loss is much higher
than that calculated from vented gas
measurements. The rate of water loss from the
battery decreases as the battery transforms from
flooded state to starved state. Because of this
change in the electrolyte condition, which is
inherent to VRLA battery technology, life
estimates based on water loss is not a straight
forward calculation.
Introduction
Dry out, a common failure mode of VRLA
batteries, occurs as a consequence of permanent
water loss. The rate of water loss has been widely
used as a method to estimate battery life.
Recently, Feder and Jones [ l ] presented a
comprehensive analysis of the literature data for
VRLA battery life estimations. Their review
noted that the published data is wide spread and
the predicted battery life varies by three orders of
magnitude. The discrepancies are proposed to be
(a) lack of a suitable method to accurately
determine the corrosion rate of the positive grid,
and (b) experimental difficulties in getting reliable
gas analysis and weight loss.
These problems were addressed in an earlier paper
presented by the author [ 2 ] .In that paper, it was
shown that it was possible to separate
quantitatively and determine accurately the
cathodic and anodic processes occurring in a
VRLA battery. These processes including the
oxygen recombination and the grid corrosion of
the positive electrode were studied as a function
0-7803-5069-3 /98/$10.00 01998 IEEE
of the electrolyte condition, with the battery
transforming from a flooded to a starved
electrolyte condition. Volumetric, voltammetric
and gas chromatographic techniques were used to
zyxw
separate the contributions from oxygen and
hydrogen evolution reactions, oxygen
recombination and positive grid corrosion. As the
battery transformed from flooded to starved
electrolyte condition, oxygen recombination
increased from 0% to about 80%. At the same
time, the corrosion rate increased three times. In
this paper, we discuss further the‘ various water
loss mechanisms which eventually lead to failure
of the battery. We will also discuss life
predictions from water loss estimations.
Theory
1. Water loss mechanisms
Most of the water loss in VRLA batteries is
zyxw
caused by (i) inefficient oxygen recombination,
(ii) positive grid corrosion, and (iii) water
zyx
permeation through the battery container and
cover.
zyxwvu
i. Ineficient oxygen recombination - Under
normal float charging conditions, water
dissociation occurs in the battery as shown below.
2H20 3 O2 + 4H’ + 4e-
The liberated oxygen at the positive electrode
diffuses to the negative electrode and gets
reduced. This reduction of oxygen regenerates
water and suppresses generation of hydrogen. This
reaction is known as the “oxygen recombination
process” and is key for the successful operation of
a VRLA battery. Inefficiency of this reaction will
contribute to water loss from the battery.
ii. Positive grid growth - A second cause of water
consumption in the battery is corrosion of the
positive grid. It is the leading failure mode of
79
4-2 zyxwvutsrqponm
zyxwvutsrqp
lead acid batteries, and it results in water loss
from the battery as shown in equation (2).
Pb + 2H20 + PbO2 + 4H+ + 4e-
Conjugate to this reaction at the negative
electrode is hydrogen evolution.
(2)
In flooded batteries, water is periodically
replenished during preventive maintenance, so the
life of the battery is not limited by water loss
through inefficient oxygen recombination and grid
corrosion. In VRLA batteries, however, water
zyxwvutsrqp
replenishment is usually not possible, so these
reactions result in permanent water loss from the
battery. It is estimated that the loss of 10% of the
total water content in the battery can result in a
20% drop in the ampere-hour capacity of a
telecom battery [l].
iii. Water permeation - A third cause of water
zyxwvuts
loss is water permeation through the battery
container and cover. Water permeation largely
depends on the nature of the plastic material used
for the battery housing. A detailed discussion for
water loss through the battery housing can be
found in a paper by Vaccaro and Klatte [3].
2. Calculations of water losses
Assuming the water vapor carried by the venting
gases is minimum, the water loss ( HZOT,,~~
) can
be determined as shown below.
Where,
H20~otal= Total water loss from the battery
H2OI.E.R.c.= Water loss through inefficient
recombination
H20corr, =Water loss through corrosion of
positive grid
H20pem, =Water loss through permeation
through the plastic housing of battery
H201.E.R.C.can be calculated from the oxygen
vented from the battery whereas H20corr.can be
calculated from the corrosion current. Procedure
for the accurate determination of oxygen
80
recombination and positive grid corrosion rates
have been discussed in reference [2]. Water loss
due to water permeation was calculated as
explained in reference [3].
According to equation (4), water losses H20 I.E.R.C.
and H20Perm.result in battery weight loss.
However, according to equation (2) water loss due
to H20corr.does not result in equivalent weight loss
since Pb consumes oxygen from water to form
heavier Pb02. Therefore, experimentally
measured weight change in a battery on float is the
net difference between two components: (a)
weight loss due to water losses and (b) weight
gain due to positive grid corrosion. Thus,
experimentally-measurable weight loss is not a
direct measure of the amount of water loss. In
order to get the total water loss from the battery
(Wt loss H20), the measured weight loss (Wt
loss,,,) has to be corrected by the weight gain
caused by positive grid corrosion.
Wt loss H 2 0 = Wt loss net + Wt gain (5)
Where,
Wt loss net = weight loss of the battery as
measured
Wt loss H 2 0 = weight loss due to total water loss
Wt gain = weight gain due to
positive grid corrosion
Experimental
All the experiments were carried out on a 12V,
125 AH battery, which was floated at 65 OC at
2.27 Vkell. Compositional analysis and volume
measurements of gases vented from the battery
were made as the battery aged. Further
experimental details can be found in reference [2].
As evident from the results in reference [2], the
nitrogen contribution in the gas collected was
negligible, indicating that the leaks' in the gas
collection setup were negligible. In addition to the
volumetric, voltametric and gas compositional
zyxwv
analysis measurements, we calculated weight loss
by taking the weight of the battery at regular
intervals during the accelerated aging of the
battery. The accuracy of the balance was within
+1 gram.

The value for the water permeability coefficient
for polypropylene was obtained from reference
[4] where the results of water permeability of
polypropylene samples cut from the actual battery
container were presented. The value for the water
permeability coefficient used for the water loss
calculations was 2.5 x g/(cm hr mmHg) [41
and was assumed that the water permeability was
independent of the float time and the battery
aging.
4-2 zy
increase in the corrosion current is due to
depolarized negative electrode. In constant float
voltage applications, such as in telecom standby
applications, the potential drop at the negative
electrode must be compensated by the
corresponding increase in potential at the positive
electrode [5-71. The increase at the positive
electrode potential results in increase in the
corrosion current [2].
In figure 2 water loss due to inefficient
recombination is plotted as a function of the float

zyxwvutsrqp
Results and Discussion
1. Rates of water loss
In figure 1 the corrosion current and oxygen
recombination efficiency are plotted as a function
of the float time at 65 OC while the battery was
time at 65OC. When the battery is in flooded
condition (approximately for the first 100 hours)
the recombination efficiency is almost 0% and the
water loss due to that reaction is at maximum. The
recombination efficiency increases as the battery
begins to dry out. For comparison, the float
current was converted to water loss (assuming all
the current goes into the electrolysis of water) and

zyxwvutsr
plotted on the same graph. Since the
recombination is very poor in the beginning, most
Float and corrosion currents
and oxygen recombination

zyxwvutsr
zyxwvutsrq
efficiency% Water loss through
2. a recombination i~ffiiiencvy
2
1.8
1.6
$j- 0.001
a
+r 1.4 EU)
=
eL 1.21 0.00075

zyxw
U)

5 0.8 -t
0
o.ooo6
0.6 0.00025
0.4
0.2

zyxwvuts
0
0 200 400
Time on float Q 6S°C, Hrs

Figure 1: Float and corrosion currents and

oxygen recombination efficiency as a function of
float time at 65 OC and 2.27 V/ cell. For clarity the
0
I
I
I

100 200 390 400

l

Time on float d 65 C, Hrs

1

Figure 2: Calculated water loss from float current

corrosion current is multiplied by a factor of 5.
floated at 2.27V/ cell. For comparison, the float
current is also shown. As the battery ages, battery
changed from a flooded state to a starved
condition. In starved electrolyte condition, oxygen
recombination is promoted at the negative
electrode. The increase in oxygen recombination
efficiency can be seen in figure 1. The corrosion
current also increases after 200 hrs of float. The
and inefficient oxygen recombination.
of the float current results in the electrolysis of
water. As the battery becomes _starved,
recombination begins to take place and the gap
between these two curves increases. The gap is a
measure of oxygen recombination occurring in the
battery.
Figure 3 shows the cumulative weight loss of the
battery as it is floated at 13.62V (2.27Vkell) and
65OC. As it can be seen from the plot, weight loss
rate is decreasing with float time. The weight loss
rate in the beginning is high and drops off to a

81
4-2

zyxwvutsrq
zyxwvuts
zyxwvuts
in the battery. The water loss through inefficient
Battery weight loss oxygen recombination is high when the battery is
0.8 T flooded and decreases to about 113 of the initial

B
E
M

OS3
zyxwvuts
zyxwvutsr
0.7
0.6
0.5
8 0.4
value as the battery becomes starved. The total
water loss rate is high for the first 100 hrs. As the
battery becomes a recombinant battery, water loss
rate decreases dramatically.

From figure 4 the rates of water losses due to

inefficient oxygen recombination, corrosion and

*
zyxwvutsr
T 0.2 water permeation are converted to percentages
0.1 of the total calculated water loss and plotted as a

zyxwvutsrq
function of the float time in figure 5 . When the
battery is in a flooded state, 80% of the water loss
0 100 200 300 400 is through inefficient oxygen recombination.
Time on float @ 65OC, Hrs Water loss through corrosion is about 10% in the
flooded state and increases to about 30% in the
Figure 3: Battery cumulative weight loss as a starved state. The contribution from water
function of the float time at 65OC. permeation increased from 14% in flooded stage
to about 20% in starved state.
lower rate as the battery becomes starved over
time.
Rate of water loss%
Rate of water losses
0.0008
U) 0.0007 201. E. R .
\ ~

?!0.0006
U)

- 0.0005
3 0.0004
3
r 0.0003 0 100 200 300 400
0
g 0.0002 Time on Float @ 65OC. Hrs
K
0.0001
0 Figure 5: Calculated water loss rates for
0 100 200 300 400 inefficient oxygen recombination, corrosion of
Time on float 0 65OC, Hrs positive grid and permeation of water through the
plastic container as a function of float time. The
Figure 4: Rate of calculated water losses from data is the same as in figure 4. For more details
gas measurements as a function of float time. see the legend for the figure 4.
~ ~Total water loss, (H201 E R c ): Water
( H z O T ):
loss due to inefficient recombination, (HzOcorr): The rate of net weight loss (Wt loss,,,) between
water loss due to corrosion of the positive grid, each battery weight measurement (from figure 3)
(H20Pem): water loss through water vapor is plotted in figure 6 . Corrosion corrected weight
permeation. loss (Wt loss H20)and the rate of calculated water
loss ( H ~ O T from
~ ~ ~ gas
) measurements are also
In figure 4 the results of the water loss through
plotted in the same figure. All these water loss
various mechanisms are depicted. It is assumed
rates are high in flooded state. As the battery
that the water permeation through battery housing
becomes starved, oxygen recombination increases
is independent of float time and battery aging. The
and it reduces water loss from the battery.
water loss through corrosion is in the same order
as the water loss through plastic case permeation

82
 4-2

zyxwvutsrqp
zyxwvutsrqpo
zyxwvutsrq
0.001
Rate of water loss
gas venting is more than two times in flooded state
compared to the starved state.

zyxwvu
.r? Gas venting rate

zyxwvutsrqpo
0 0.0009
6 80
0.0008
-U)
0 70
$ 0.0007
c
m 2 60
w-
0
0.0006 3 50
C I

zyxwvutsrq
3 0.0005 40
2 -c@
~ ~ i '
0.0004 30
I

zyxwvutsrq
I I I
0.0003 I
0 100 200 300 400
Time on float Q 65'C, Hrs
Figure 6: Rate of calculated water loss (H*OTod,
from the gas measurements), measured weight loss
(Wt lossnet,from the weight loss measurements),
and corrosion corrected water loss (Wt
from weight loss measurements) as a function of
float time.
As explained earlier, the difference between the
two weight loss plots is equal to the water loss due
to positive grid corrosion. The water loss
contribution from the corrosion is about 7% of the
measured weight loss (Wt loss,,,) in flooded
condition and it increases to about 40% in starved
state.
The difference in the total calculated water loss
(H20Total)and the corrosion corrected weight loss
+
0
0 100 200 300 400
lime on float @ 65OC Hrs
Figure 7: Gassing rate as a function of the float
time at 65OC.
Contribution from high rates of water permeation
through battery housing can also be another
source. High rates of water permeation is possible
under flooded electrolyte condition due to higher
water vapor pressure in side the battery.
Water vapor loss can be measured only by
weighing the battery and not through the gas
analysis set-up used in the present study [ 2 ] .
2. Float life estimates

(Wt is high in the beginning and
decreases with float time. The close agreement of
these two values after the battery reaches the
starved condition reinforces the validity of the
method and the accuracy of the gas measurements.
In flooded state the rate of corrosion corrected
weight loss calculated from the weight
measurements is higher than the total water loss
calculated from the gas measurements (see figure
6). This difference is probably due to higher water
vapor losses through vent. Water vapor pressure
always exists in the battery at any given
temperature .[8]. The water vapor losses will be
high in flooded condition because vent opens
frequently. The frequency of vent opening
depends on the pressure buildup within the battery
which also controls the venting rate of the gas.
The gas venting rate is plotted as a function of the
float time in figure 7. It can be seen that the rate of
zyxwv
Weight loss measurements have been widely used
to estimate the float life of the battery [I]. In these
estimates water loss was assumed to be the same
as the weight loss of the battery. However,
according to equation (3, the weight loss as
measured should be corrected for the contribution
from the weight gain from the positive grid
corrosion in order to calculate accurate water loss.
Comparison of the weight loss curves before and
after correcting for corrosion from figure 6 shows
that the weight contribution for the corrosion can
vary from 7% in flooded state to 40% in starved
state. In the present study the corrosion rates
calculated are for the pure lead grids. If the
positive grids are made of lead alloy, higher
corrosion rates can be expected. It is evident from
these studies that the battery weight losses as
measured can not be used for water loss

83
4-2 zyxwvutsrqpon
zyxwvutsrqp
calculations without accounting for the weight
gain due to corrosion of the positive grid.
Corrosion of positive grid strongly depends on the
electrolyte condition as demonstrated in earlier
study [2] and can increase by three times when the
zyxw
electrolyte changed from flooded state to starved
condition. Therefore, it is important to determine
in situ corrosion rates accurately under actual float
operating conditions in order to calculate reliable
water losses from the battery.
A typical VRLA battery under goes electrolyte
changes from flooded, wet, moist, and dry state as
explained in the reference [9]. As seen in this
study the water loss rate depends on the state of
the electrolyte condition; it is high in the flooded
condition compared to starved condition. The life
estimations based on these water losses are not
straight forward.
Further work is in progress to see whether
accelerated testing can be used to estimate battery
float life [IO].
Summary and conclusions
Accurate determination of water losses due to
inefficient recombination and corrosion of the
positive grid of a VRLA battery floated at 65 OC
has been shown to be possible using in situ
measurements of volumetric, voltammetric and
gas analysis. Water losses through water
permeation were also computed. The calculated
total water losses thus determined are in good
agreement with the corrosion corrected weight
loss measurements when the battery is in a starved
electrolyte condition.
The unaccounted weight losses in flooded
condition is likely to be due to the higher water
vapor losses because of the frequent vent opening
when the gassing rates are higher. Gassing rate is
about two times higher when the battery is in
flooded state compared to the starved condition.
For accurate determination of water loss form the
battery, the weight loss of the battery as measured
should be corrected for the weight gain from
positive grid corrosion.
84
As evident from this study, accurate determination
of the water loss from a VRLA battery is possible.
However, float life estimations based on this value
is not straight forward, since the rate of water loss
from battery is not constant and never gets
stabilized in the entire lifetime of the battery.
Acknowledgments
The author gratefully acknowledge S . Klaren for
his support for the experiments and C. Mak, S .
McCluer, F. Laman and P. Ng for helpful
discussions.
References
[I] D. 0.Feder and W. E. M. Jones
Proceedings of INTELEC 96 PP. 184.
[2] C. S . C. Bose and Greg Mathiesen
Proceedings of INTELEC 97 PP. 13.
zyxw
[3] F. J. Vaccaro and J. A. Klatte
Proceedings of INTELEC 89 pp 6.4,
[4] W. R. Lambert et. al.
“Water vapor permeability of plastics for valve
regulated lead acid batteries” - BLOl11740-
95 1013-22TM, AT&T Technical Memorandum.
[5] J. A. Magyan, M. K. Kepros and R. F. Nelson
J. Power Sources 31(1990), 93.
[6] W. B. Brecht, The Battery Man (1998) 24.
[7] D. Berndt and U. Teutsch
J. Electrochem. Soc., 143 (1996) 790.
[8] D. Berndt in “Maintenance-Free Batteries”,
Second edition, 1997, Research Studies Press
Ltd., Taunton, England.
[9] W. E. M. Jones and D. 0. Feder
Proceedings of INTELEC 95, pp. 154.
[IO] F. Laman et. al., to be presented at
INTELEC 98.