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LEAD-ACID BATTERY CHARGING BY CURRENT PULSES. DOES IT HELP TO

REDUCE SULPHATION?

Conference Paper · October 2003

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Adolfo Perujo Kevin John Douglas

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 LEAD-ACID BATTERY CHARGING BY CURRENT PULSES. DOES IT HELP TO REDUCE SULPHATION?

A. Perujo and K. Douglas

E.C. DG-Joint Research Centre. Institute for Environment and Sustainability. Renewable Energies Unit.
Ispra (Va), 21020 Italy.
Tel. +39 0332 785175. Fax +39 0332 789268. E-mail: adolfo.perujo@cec.eu.int

ABSTRACT: One of the several degradation mechanisms of lead-acid batteries is the irreversible sulphation of the positive
and negative active mass. The evolution of the lead sulphate occurs during deep and prolonged discharge of the electrodes. It
has been suggested that the use of pulsed currents during the charging of this battery type will reduce the evolution of the lead
sulphate on the electrodes or will even recover the “rechargeability” of those batteries that have lost it due to very extended
storage in a low state of charge. The purpose of this paper is to present the results of experiments on the recovering of
“rechargeability” of highly sulphated lead-acid batteries by using high frequency pulsed-current charging. In PV and other
RES applications where the battery might be left for long periods in a low state of charge the use of pulsed-current charging
may increase the battery lifetime; hence the adoption of this battery management approach needs to be considered as an option
in PV applications.

KEYWORDS: 1:Lead-acid battery. 2: Sulphation. 3: Rechargeability

1 INTRODUCTION 2. EXPERIMENTAL SETUP AND PROCEDURE

Lead-acid batteries are the most frequently used
technology as electricity storage both for automotive and
renewable energy systems (RES) applications, and in
particular for stand-alone PV applications. PV systems
impose operating conditions on the battery that are quite
different to those of automotive applications and in
particular, the PV battery operation at low state of charge
(SOC). In many situations, the batteries are left for a
prolonged period at low SOC with the subsequent
evolution of irreversible lead sulphate (sulphation) on the
electrodes. This irreversible sulphation has been identified
as one of the major ageing/failure effects in PV systems.
The sulphation affects predominantly the positive
electrode [1].
The use of pulsing currents during charging has been
suggested as a method to reduce the evolution of the lead
sulphate on the electrodes [2] and that will even recover
the “rechargeability” of those batteries that have lost it due
to a very extended period in a discharged stage. Here
“rechargeability” is understood as the ability of the battery
to accept charge. Extensive investigations of pulsed
currents have also been performed in battery charging
schemes to allow for very short recharging times [3]. The
reduction of battery production cost by using pulsed
currents has also attracted large interest [4,5] as it is
expected that pulsed current formation may allow for an
increase in faradic efficiency and/or reduction in the time
of formation. Diniz et al. [5] have studied different pulsed
current formation conditions for positive plates,
concluding that longer formation times and low
frequencies (for short formation times) are the best
conditions in terms of PbO2 yield.
In this paper we report the initial findings on the use of
pulsed-current charging to regain “rechargeability” of
highly sulphated lead-acid batteries under laboratory
conditions and also argue on the reasons for this recovery
of the studied batteries.
Eight lead-acid batteries heavily sulphated due to their
storage for a long period in the discharged state were
obtained from the PV system that they were serving. The
2V batteries are OPzS mono blocks with a nominal
capacity (C10) of 450 Ah. The positive electrode is tubular
with the active mass made with low antimony content,
while the negative electrode is of the pasted grid type.
2.1 Battery Testing Facility
The battery testing system in service in our laboratory
comprises a Solartrom 1470 Multichannel Battery Test
System combined with eight Dataline 290 power-boosters.
The system is fully computer-controlled through a host PC
running CellTestTM software. It has been specifically
designed to provide accurate data at high throughput and is
optimised for multi-channel high-speed pulse and
impedance tests on batteries, supercapacitors and fuel cells.
Constant voltage, current, power and load test strategies are
available. The system makes use of analogue control loops
for smooth control of the applied signal. The maximum
applied levels are up to +10V, -3V and at least 4A per
channel. Its coupling with the power booster allows the
system to provide our required voltage and current ranges
(±50 V and 25 A).
The multitasking facility of the operating system allows
data acquisition tasks to run in parallel with user interface
software, to ensure that data is collected at the required
rate. The software allows multiple projects to be set up and
all active projects permanently acquire data while their
schedules are running. The high-speed characteristic of the
battery testing system allows for high frequency current
pulse charging of the batteries with a large flexibility to set
the amplitude, period and repetition rate of the pulse.
For routine capacity measurements, a fully computer
controlled system based on bipolar amplifiers (±20 V, ±20
A) were used in order to release the most sophisticated
system for the continuation of the pulsed-current charging
of the other batteries.
 All the batteries are kept in a temperature-controlled the battery is reached. While in the case of battery (b) the
bath during the experiment in order to eliminate the high voltage safety limit for the battery (2.5 V) is reached
possible influence of the temperature on the final results. with a very low charging current triggering the security
stop of the battery charging programme. This indicates the
2.2 Experimental Procedure inability of both batteries to accept the charge.
Initial recharge of the eight batteries was attempted by
using a standard method (IEC 896-1 [6]) to confirm 2,4 0,6
whether the batteries were able to maintain their charge. If
2,2 (a)
there was an immediate voltage drop as soon as the 0,5
charging unit was disconnected from the battery then 2,0 (b) (b)
pulsed-current charging was applied. In fact, immediate 0,4
1,8

Current (A)
Voltage (V)
overcharge was observed even at very low recharging (a)
currents. So, all the eight batteries that behaved in this 1,6 0,3

fashion were used with the pulsed-current charging 1,4 0,2

technique in an attempt at their recovery, as described
below. 1,2
0,1
Several pulse profiles, without depolarisation current, 1,0

were tested in order to recover the “rechargeability” of the 0,8

0,0
batteries. Fig.1 shows the shape of the pulse and the 12:00:00 12:01:00 12:02:00 12:03:00
Time
parameters that define the pulses. Here ‘pulse profile’
refers to the ratio between the time with current switch on
and the time with current switch off; i.e. dwell/(period- Figure 2: Initial behaviour of two batteries. Battery (a)
dwell) in figure 1. accept a low charge while battery (b) reaches the
voltage high limit very quickly, triggering the
security of the testing facility

Several pulse profile combinations were attempted

(trial and error) in order to find the combination that
attained “rechargeability”. Many of these combinations
resulted in the batteries reaching too high voltages,
therefore the strategy was to keep the pulses with small
Pulse amplitud

profiles, i.e. short time at these high voltages levels, in

order to avoid further (different) damage to the battery.
The pulse profile combination that provides better results is
described in Table 1. This combination includes 11 steps
with 8 different pulse profiles that repeat for at least 10
0 times with ever increasing amplitudes from 0.5A to 20A.
Dwell The amplitude for some of the batteries under study could
Period
be increased more quickly up to 20 A if that particular
battery was not heavily sulphated.
Figure 1: Pulse profile used in this work. All the pulse
profiles were without depolarisation current. Table 1 Pulse-profile combination that resulted the best for
recovery of the “rechargeability” of the batteries under
Several different currents and profiles were study. The amplitude is of 10 A for all the steps although it
investigated during the present work. The pulses had could be increase to 20 A if the sulphation of the battery
amplitudes that varied from 0.5 to 20 A and pulse dwell was not too heavy.
times ranging from 0.0001 to 10 sec. During the charging
period, current and voltage monitoring was performed in
Dwell Period
order to check for the “rechargeability” of the batteries. Step Notes
time (s) (s)
Once the recovery was attained, periodic capacity
1 1 min. wait
measurement of the batteries were performed to check for
the level of capacity regained. Loop starts run once repeat at least 10 times
2 0.0001 1 Step duration 2 min
3. RESULTS AND DISCUSSION 3 0.001 1 Step duration 2 min
4 0.01 1 Step duration 2 min
The batteries used in this study were visibly heavily 5 0.1 1 Step duration 2 min
sulphated, but to different degrees. They had initial 6 1 5 Step duration 2 min
voltages of approximately 0.9V with an electrolyte density 7 2 5 Step duration 2 min
of 1.0. They all reached immediate overcharging at 6 3 5 Step duration 2 min
minimal recharging currents. This can be seen in Figure 2 9 5 10 Step duration 2 min
where the behaviour of two of the batteries is depicted. In 10 1 min. wait
the case of battery (a), which was visibly in a better state Loop ends
as compared with battery (b), a small charge acceptance is
11 5 min. final wait
obtained, although nearly the maximum voltage level for
 After subjecting the batteries to the pulse-current
charging described above all the batteries were able to
keep their charge. As their voltage reached and maintained
more normal values (of about 1.7V) the current pulses
were increased to longer dwell times (such as 10s for a
one-minute period). Figure 3 depicts an example of a
battery response to one of these pulse profiles with longer
dwell times (10 A amplitude with a dwell of 10 s). The
battery responds by diminishing the voltage as the time
passes until it reaches voltages close to those expected by
a healthy battery being charge at 10 A. No significant
increase in the temperature of the batteries was observed
during the pulsed-current charging.
12
10
8
Volts
6
4 many different processes are taking place. During
2 process from the electrode and lead sulphate has to deposit
0 in the immediate vicinity of where the ions are formed.
0:00:00 6:00:00 12:00:00 18:00:00
Time (hours)
Figure 3: Effect of current pulses of 10 A with a dwell
time of 10 s on charge behaviour. As the time
passes the maximum voltage converges versus
values nearer to those expected for a "healthy"
battery.
All the batteries were then subjected to capacity tests
and were found to retain their charge even after a
prolonged rest period (up to four months) of storage. The
“rechargeability” levels were different for each of the
batteries indicating varying initial amounts of sulphation.
Figure 4 shows the capacity measurement [6] on one
of these batteries where it is evident the ability of the
battery to accept charge. Indeed the charge factor (Ah
charge/Ah discharge) at different charging regimes is
nearly unity. It is also apparent that although the battery
has not fully regained its nominal capacity (C10 =450Ah)
it has recovered a reasonable amount. Hence, it can be
installed once again for its envisaged use.
The use of this sort of pulse charging as a method of
recovering “rechargeability” has the advantage of not
imposing high charge factors on the battery. This avoids
the subsequent possibility of either having water
loss/drying out, temperature rise (even thermal runaway),
increased corrosion, an increase of active mass shedding
or a combination of the above. Due to the nature of the
pulse (pulses without depolarisation), the battery does not
undergo a high throughput and therefore it does not suffer
from further capacity losses as indicated in [8] due to
microcycles (i.e. polarity reversal of the battery current
with periods less that a minute). These microcycles are
typical of batteries operating in combination with inverters
in renewable energies systems (RES).
450
0.1xI10 CHARGE 0.4xI10 CHARGE
300
Capacity (Ah)
150
0
-150
0.1xI10
-300
RESIDUAL 0.1xI10 DISCHARGE DISCHARGE
CAPACITY
-450
0 2 4 6 8 10 12 14
Days
Figure 4: Capacity measurement of one of the batteries
after recovering "rechargeability" and being
stored for 4 months. The battery has recovered a
large part of its capacity.
During charging and discharging of lead-acid batteries
discharge, lead ions have to be formed in a dissolution
These processes are very quick. When the battery is left in
the discharged state (very low SOC) the formed lead
sulphate crystals tend to be quite large making the charging
process very difficult. Fast charge-discharge cycles will not
result in electrochemical conversion, as the behaviour will
be completely capacitive (due to the effect of the double-
layer capacitance) above certain frequencies. However, the
pulse profile imposed on the batteries in this work are
without depolarisation and therefore it is possible that
electrochemical processes can take place. This results in
changes in the microstructure of the electrodes due to
inhomogeneous current distribution because of different
electrical resistance and electrochemical potential. It is also
possible that by imposing large current pulses for small
dwell times at the beginning of the proposed procedure the
lead sulphate crystals will be reduced in size because the
atoms in the molecule increase their energy levels to a
point where the molecular bond can be broken. However,
we cannot provide conclusive experimental evidence for
this assumption at the moment. A hint that this could be the
case can be found in that at the beginning of the pulse
profile imposed on the battery, large voltage levels and
reduced charge efficiency are reached. This is compatible
with the presence of large lead-sulphate crystals. As the
time evolves the voltage levels reached are decaying and
the charge efficiency increases; this is also coherent with
the appearance of smaller lead sulphate crystals (see figure
3). Subsequently these small lead sulphate crystals dissolve
more quickly because the ratio of surface area to volume is
larger, allowing rechargeability of the batteries.
The other possible explanation to the recovery of
heavily sulphated batteries by this method is similar to that
of the case of battery formation by the use of pulsed
current. By using pulsed formation the tetrabasic lead
sulphate-rich positive plate is converted more efficiently
into PbO2 than in the case of continuous current formation.
It has also been reported [5] that lower frequencies with
longer periods with the current off leads to higher
conversions to PbO2. The authors’explanation is that as the
current is applied, the electrochemical reaction converts
 lead sulphate to lead dioxide and sulphuric acid. With
increasing concentration of sulphuric acid, formation
efficiency is reduced. When the current is off, sulphuric
acid is then diffusing away from the plates, as the pulse
starts again, acid concentration is lower and therefore
higher formation efficiency is achieved. The authors argue
that efficiency is controlled by sulphuric acid diffusion.
This case is quite close to our pulse profile where we have
in some sense low frequencies with relative long periods
with the current off. So, the mechanism of recovering
rechargeability of the battery can be similar to that of the
battery formation by pulsed current.
The possibility of reducing the internal resistance and
therefore increasing the charge acceptance due to pulsed
current cannot be eliminated as a possible mechanism for
the recovery of rechargeability; as the slope of the voltage
increment lowers when the duration of the rest period
increases after a pulse [7]. Although, in this instance, the
authors studied the case with a depolarisation pulse that is
not the situation in our study.
Further investigations need to be performed in order to
elucidate which one of these possible mechanisms is
providing the recovery of rechargeability in heavily
sulphated batteries.
REFERENCES
[1] F. Mattera, D. Benchetrie, D. Demesttre, J.L. Martin,
E. Potteaus. J. Power Sources 116 (2003) 248.
[2] Apparatus for charging and desulfating lead-acid
batteries. U. S. Patent No. 6,184,650.
[3] S.C. Kim, W.H. Hong. J. Power Sources 89 (2000)
93.
[4] L.T. Lam, H. Ozgum, O.V. Lim, J.A. Hamilton, L.H.
Vu, D.G. Vella, D.A.J. Rand. . J. Power Sources 53
(1995) 215.
[5] F.B. Diniz, L.E.P. Borges, B.de B. Neto. . J. Power
Sources 109 (2002) 184.
[6] International Electrotechnical Commission (IEC):
International Standard IEC896-1. Stationary lead-
acid batteries: general requirements and methods of
test.
[7] S.C. Kim and W.H. Hong,. J. Power Sources 89
(2000) 93-101,
[8] A.L. Ruddell et al. J. Power Sources 112 (2002) 531-
546.

4. CONCLUSIONS

Using pulsed current as a charging method increases

the charge-acceptance of batteries. This method of
charging not only allowed performing high-rate charging
as some commercially available charging unit claims, but
also it seems to allow recovery of the “rechargeability” of
highly sulphated batteries. This can be achieved without
undue overcharging and the subsequent higher
temperatures that can lead to increased corrosion.
Further in depth investigations are needed to elucidate
the electrochemical basis of this recovery. Some plausible
explanations exist:
1. The reduction of the internal resistance due to the
current pulse.
2. Increasing the energy level of the atoms in the
sulphate molecule to a level where the bond can be
broken and the atoms are converted to a free ion in
the electrolyte
3. Control of the charging efficiency due to the
diffusion of the sulphuric acid governed by the cyclic
application of current pulse with long rest times in
between.
In PV and other RES applications where the battery
might be left for long periods in a low state of charge the
use of pulsed-current charging may increase the battery
lifetime; hence, the adoption of this battery management
approach needs to be considered as an option in PV
applications.

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