besttesting 41

Formation pulse charging

Reducing energy usage is a key factor in developing cleaner
greener batteries for a carbon-sensitive economy. Picking up
where the successful connector testing series left off, BEST’s
technical editor, Dr Mike McDonagh introduces the development
of an improved formation programme for lead-acid batteries.

T
his is the first report on the sophistication of the process
new testing programme and monitoring equipment,
undertaken by the same Fig 1) is that more energy is
team that successfully completed pumped into the batteries in a
the formation connector shorter time. This causes heat,
improvement project reported and increases the rate of gassing
in the last edition of BEST. The and other parasitic reactions,
team are now concentrating on which absorb increasing
improving the formation method amounts of energy that should receives an electrical charge.
itself. This process is largely go into converting the active Before this charge the two
unchanged since I began in the material into the finished form. electrodes are electrochemically
industry over 40 years ago and is The first project was concerned identical. This means that
still a bottleneck with low energy with the variability of connector there is no energy or potential
efficiency. This is particularly true resistance in service. For obvious difference between them.
of today’s practice, which, in SLI reasons, it was necessary to This does not give the valence
manufacture at least, is reduced resolve that issue before this electrons in the lead compounds
to 12 to 24 hours from the 24 to new project, to improve the any impetus to move from one
48 hours that I was introduced to energy efficiency of the process, electrode to the other. It is
all those years ago. could begin. necessary then, to create or form
The main difference between The formation process is the anode, and the cathode,
then and now (apart from the the first time that the battery from the manufactured green
Fig 1: Modern process and monitoring equipment display. Digatron formation rectifier and digital USB plates after they are filled with
oscilloscope the sulphuric acid electrolyte.
Hence the word ‘formation’ for
this battery process.
The standard method of
formation is as old as the
battery chemistry, and relies,
for the main part, on pushing
in a certain number of Ah in
order to ensure the materials
are transformed from the basic
sulphates, oxides and metal,
into the lead-dioxide positive
and pure-lead negative plates
with which we are familiar. The

bestmagazine // Spring 2021

42 besttesting
formation reaction, or rather
reactions, of cured active
material soaked in electrolyte,
can be simply summarised:
Positive:
PbSO4 + PbSO4.H2O +
PbSO4.3H2O + Pb3O4 compounds
+ lead are oxidised to PbO2
Negative:
PbSO4 + PbSO4.H2O +
PbSO4.3H2O + Pb3O4 compounds
+ lead are reduced to Pb
This is traditionally a time
and energy consuming process.
In theory all you need to do
is to pump electrons into the
negative whilst drawing them
out of the positive plates. The
coulombs necessary for the
theoretical conversion can be
calculated using mole fractions
of all of the various compounds.
This is a simplistic view and
it assumes 100% conversion,
which does not happen, in the
first charging process. In fact,
most batteries, particularly
SLI, are sold with around 85 to
90% conversion of the active
material. This leaves some
sulphate in the plate, which
gradually becomes converted
during subsequent charging in
service.
Current formation methods
The simple fact is, the
theoretical ampere-hour
requirement will not go
anywhere near to providing the
number of coulombs needed
to make a practical, adequate
conversion of the materials.
The reason is due mostly to the
inefficiencies of the process,
created by the parasitic side
bestmagazine // Spring 2021
The simple fact is, the
theoretical ampere-hour
requirement will not go
anywhere near to providing the
number of coulombs needed to
make a practical, adequate
conversion of the materials”
reactions, along with physical
and chemical properties of
the materials being converted.
These aspects have been
covered in previous editions of
BEST, but here is a summary:
Physical and chemical
limitations
1. Active material particle shape
and surface area:
The reactions that transport
sulphate out of the particles
during charging are largely
solid state, which makes the
process slow and inefficient.
Part of the active material is
used to create a conducting
and mechanically robust
framework to give it rigidity
and conductivity. This amount
of AM is lost in providing the
Ah capacity of the battery.
2. Concentration effects of the
electrolyte at the solid/liquid
interface:
There are non-equilibrium
reactions at the solid/
liquid interfaces, which
create shifting concentration
gradients. As more sulphate
is rejected from the AM
particles into the electrolyte,
the concentration of the dilute
sulphuric acid increases with
time on charge. This means
that the driving force for the
conversion of lead sulphates
to lead dioxide and lead
requires more energy, or it
takes longer.
2PbSO4 + 2H2O →
Pb + PbO2 + 2H2SO4 eq 1
This leads to an increase
in H2SO4 concentration in
the electrolyte. This, in turn,
reduces the driving force for the
conversion of active materials
into the positive and negative
electrodes.
Parasitic reactions
As the voltage of the cell
or battery increases with
increasing acid concentration
in the electrolyte, other non-
AM converting reactions
are triggered. The two main
coulombic grabbing reactions
are:
Water electrolysis
H2O → 2H+ + 2e- + O2- eq 2
Gas evolution
2H+ + 2e- → H2
O2- → ½O2 + 2e- eq 3
These reactions along with the
increasing back-EMF increase
the IR of the cell, which creates
heat due to the I2R effect of a
circuit.
Strategies to overcome
inefficiencies
It is fairly clear that this
process will neither be efficient
nor trouble free. However, a
more in-depth analysis does
show that there is scope to
alleviate some of the energy
sapping factors. The effects

of increasing electrolyte
concentration and gas evolution
can be mitigated by the simple
expedient of pulsing. This has
been covered to some extent
in several articles in BEST,
both for battery recharging and
battery formation. In the case
of the concentration gradient, a
constant-current pulse initiates
the charge reaction of Eq 1
above. The voltage rises. That
then triggers the secondary and
parasitic reactions. It should
then be simple enough to limit
the pulse width to prevent the
voltage rise. Unfortunately,
the rising SG of the electrolyte
means that the rest voltage
(current = 0) of the lead-acid
cell will also rise. At some point
it will be close to the water
breakdown and gas evolution
potentials. This will mean that
the proportion of the pulse
actively converting the AM to
the charge state will decrease
as the SoC rises. Additionally,
the surface concentration
effects also mean that the
voltage will rise faster and
deteriorate more slowly as
the electrolyte concentration
increases with SoC.
For this reason, the pulsing
has to be intelligently linked
to the progress of the AM
conversion in the cell during
the time of the formation
programme or schedule. This
is less of a problem with acid
recirculation methods that, if
applied correctly, will keep the
electrolyte concentration at a
low level during the process.
However, for standard, flooded,
container-formed batteries the
main concern is heat generation
and keeping the batteries
besttesting 43
The unit is programmable
and, as well as enabling a great
array of battery testing
procedures, it can simulate
virtually any application and
any manufacturer’s formation
programmes”
cooled. In this case pulsing can
help to reduce the amount of
gas being formed and also the
heat build-up and consequent
temperature rise from these
exothermic, parasitic reactions.
Although the voltage build-up,
on and off charge, is increasing
for the pulsed method as well as
for the linear charging principle,
there is a lag between attaining
the gassing voltage during
the pulse, and the evolution
of the gas on the AM particle
surface. This lag is variable
depending on the SoC of the
battery and the chemistry of the
active material. The grid alloy
composition and the additives
to the active material affect the
specific chemistry relating to
gas evolution during the paste-
mixing step.
In essence, we are using the
factors described above to design
a formation programme that will
reduce the current energy input
by making the energy input and
AM conversion more efficient.
The efficiency essentially
depends upon minimising the
parasitic side reactions resulting
from the battery voltage during
the charging portion of the
pulsed current. The basis of
designing an effective pulsed
formation programme will be the
minimising of non-productive
reactions combined with
maximising the coulombic input
to the active material conversion
reactions. However, there is a
price to pay for this efficiency: it
is the amplitude of current pulse
required to put sufficient Ah into
the AM, when there are periods
of zero current. Due to this we
need to increase the current in
proportion to the pausing time.
This is not as bad as it seems,
and work already done shows
that far fewer Ah are needed
because the process is more
efficient.
Current work
As described in previous
articles, UK Powertech has
allocated a laboratory facility
for electrical testing. Digatron
have contributed to this by
providing one of their state-
of-the-art electrical test units
(BNT 150/036-4ME). This has
four outlets, each providing a
36V, 150A, fully programmable,
charge-discharge capability. The
unit is programmable and, as
well as enabling a great array of
battery testing procedures, it can
simulate virtually any application
and any manufacturer’s
formation programmes. The unit
is able to capture, store and
export test data for subsequent
manipulation and analysis. It can
even provide a range of pulsed
constant current output signals
for the trials. However, this
option does present a particular
challenge for this series of
test programmes— that is the
accurate recording Ah and Wh
with a high frequency pulsing
system.
bestmagazine // Spring 2021
44 besttesting
The problem lies in the
data registration commands,
and unless a data point lands
exactly on the on-and-off
position in pulsed operations
then the data recording will not
accurately reflect the energy and
ampere hours consumed in the
programme. This is true of any
equipment, and with previous
testing of pulsed battery
charging we knew that unless
the on-off times of a CC pulse
were symmetrical it would be a
difficult task. There are solutions
to this that are being trialled
at the moment. In the interim
period we have decided to verify
the principal in a series of tests
using symmetrical CC pulses. The
results here are taken from the
Fig 2: Dr MIke McDonagh (left) and Mark Rigby at the cell and battery testing setup
bestmagazine // Spring 2021
initial phase of our programme and frequency is not ideal in
using a 1 Hz CC pulse consisting providing the most energy
of 500ms on and 500ms off. efficient method.
This allows a registration of The quantity of results
0.5 seconds per result. It also over the time of the formation
enables a simple calculation programme is massive. It has
of Ah to be made. In order caused recording problems
to calibrate the process, this and also data manipulation
calculation was compared to the problems using the spreadsheet
registered cumulative Ah from programme.
the tests, to verify the accuracy Once an alternative energy
of the method. So far there is measurement is implemented
better than 98.5 % correlation then the programmes will
between calculated and change
registered Ah. This then gives a Despite this limitation on
high degree of confidence for the pulsing, we have been able to
recorded watt-hours or energy gain reliable results showing
consumption registered during the potential for improving the
these tests. However, this gives formation process. The test
two problems: set-up is shown in Fig 2. This
The pulse morphology consists of the test cells, in
this case 2V flooded traction
cells connected to the Digatron
unit, an extraction fan, a water
bath (currently empty) and
leads attached to a digital
oscilloscope. The Digatron unit
is programmed with a variety of
formation programmes. These
range from manufacturer’s
own programmes, to the
experimental new programmes
for these trials. The
Fig 3: Voltage response of a 2V lead-acid cell to a 1Hz constant
current pulse
 besttesting 45
experimental set-up shown
is not truly representative of
in-situ factory conditions.
Understandably, having only
one cell can hardly be compared
to a full circuit of 18 SLI or
108 2V cells, however, this is
a comparison test to measure
the relative effectiveness of
the different charge regimes.
The full production trials with
participating companies will
start later in 2021.
Since the new programmes
involve pulsing are likely to
Fig 4: Standard discharge curve lead-acid cell
be in the KHz range it will be
difficult to digitally record the required to provide constant- formed. Several samples
information with the present current pulses for single cell and will be charged according
registration method. It becomes 12V battery formation. It must manufacturer’s own programmes
even more difficult when the record and display pulse current and the variation in battery
pulses become asymmetric. We and pulse voltage response, cell discharge performance will be
have adopted a symmetrical and battery temperature, watt- noted (Fig 4: standard discharge
low frequency pulse of 500ms hours accumulated and ampere- curve). This variation will be
on and 500 ms off, a total pulse hours accumulated. Accuracy of applied when analysing the
frequency of 1Hz. This is not measurements must be verified discharge results of batteries
ideal but should provide some by testing and comparison of formed by the new methods. The
measure of energy efficiency ampere-hours with calculated recording of energy and the other
improvement, at least over values. test parameters will be mostly
part of the cycle. Fig 3 shows Stage 2: assessed using the Digatron test
the voltage response of a 1 Hz Establish baseline formation unit, once the accuracy has been
CC pulse for a 2V traction cell, data for standard commercial verified. Other simpler methods
approximately 50% formed. programmes. (chiefly analogue) of recording
The main intention is to obtain Participating companies will energy used, are currently under
an understanding of how to provide samples for laboratory investigation. The pulse voltage
accurately measure energy trials and also provide their response will be measured
usage using standard Digatron standard formation programmes using the USB oscilloscope. The
test equipment. for comparison with new values of voltage and time will
The tests underway at present formation programmes. be verified by reference to the
are based on 2V traction cells Stage 3: Digatron unit power supply.
supplied green (unformed). Verification of accuracy of Stage 4:
These have a tested C4 capacity energy measurement. After the baseline data of
of approximately 56 Ah after The baseline measurements standard formation methods
full formation programme and for standard formation methods and accuracy of results has been
several 85% charge discharge described in Stage 1 will be established, the new formation
cycles. The test programme repeated with the same cell programmes will be tested
consists of the following stages: or battery types. At this stage and the results compared with
Stage 1: the only criteria for formation standard. This will continue and
Formation processes and efficiency will be the discharge the methods will be modified as
equipment— Identify equipment tests after the batteries are indicated by the test data.

bestmagazine // Spring 2021

46 besttesting
Pulse Total been established that we have
Process Description Stages
stages time enabled the use of the Digatron
Manufacturers test unit (as the power source),
Constant current fixed time 5 0 46 the pulse generator and the
standard
formation programme automatic
Pulse 1 Completely pulsed current 4 4 36
operator. This has the advantage
Pulse 2 Part constant current part pulsed 4 3 34 of accurately recording the test
Pulse3 Part constant current part pulsed 4 3 28 parameters of energy use, time
Pulse 4 Part constant current part pulsed 4 3 22 of process and temperature
Table 1: Description of formation programmes of the cell or battery under
examination, as well as running
Stage 5: Results the original factory formation
Once a suitable laboratory- To begin the new formation programmes. The sequence of
based programme has been method programme, a events has been as follows:
established, it will be trialled in participating company Establish ability of Digatron to
the formation departments of has donated unformed 2V provide a constant-current pulse.
several participating lead-acid traction cells in order to This was achieved during an
battery factories. The results begin the stage-one trials. initial trial using a 500ms on and
from these field tests will be This is the identification 500ms off constant-current pulse
used for further programme and characterisation of the programme.
modifications and further on- equipment and methodologies Accurate recording of the
site testing. The final formation required to obtain reproducible accumulated Ah and Wh by
programmes will be collated and and accurate results. Table 1 is a having 500ms data registration.
further evaluated in laboratory brief summary of the formation This was necessary to ensure
tests to be finalised for programmes tested so far in the amps and volts when on and
commercial release. the project. At this point, it has off were captured accurately.
The initial tests showed a
Table 2: Manufacturers standard programme 2V traction cells 98.5% accuracy of Ah against
Step Operator Value Limit Total Ah Total time the calculated value. Table 2
shows a typical programme and
1 CHA 5A 0.5 h 2.5 0.5 h
the calculation of the Ah. Also
2 CHA 20 A 3h 62.5 3.5h shown is the recorded value after
3 PAU 0 1h 62.5 4.5h the programme was run. With the
4 CHA 20 A 3h 122.5 7.5h amps and Ah accurately recorded
5 PAU 0 1h 122.5 8.5h it was assumed that the volts
and Wh were also accurately
6 CHA 20 A 3h 182.5 11.5h
recorded.
7 PAU 0 1h 182.5 12.5h Factory formation programmes
8 CHA 20 A 3h 242.5 15.5h were run and repeated for the 2V
9 PAU 0 1h 242.5 16.5h cells.
These gave a 7.2 x C5 factor as
10 CHA 20 A 3h 302.5 19.5h
a total coulombic input during
11 PAU 0 1h 302.5 20.5h the process. This high coulombic
12 CHA 20 A 3h 362.5 23.5h input is not uncommon for
13 PAU 0 1h 362.5 24.5h traction cells. It is less for SLI
14 CHA 7.5 A 13.5 h 463.75 38h batteries due to the higher plate
surface area— designed for high
15 PAU 0 1h 463.75 39h
cold-crank performance rather
16 CHA 7.5 A 6h 508.75 45h than maximising Ah capacity.

bestmagazine // Spring 2021

 besttesting 47
The process time was 46 hours
with measurement of electrical
data and cell temperature (Fig 5,
Table 2). There are eight stages
with seven pause intervals to
keep battery temperatures under
control. The current is less in
the latter stages of the 46-hour
programme.
Two cells were tested in this
way and the discharge results
(Table 3) show a 9% variation in
discharge performance on the
first discharge test. Fig 5: Results of manufacturer’s 46 hour formation programme, voltage, current and temperature recorded
2-volt cells were acid filled
and formed with a pulse response near the end of the programme. Likewise, the
programme over s 34-hour programme. The Wh slightly temperature and water loss
period. The temperature of the increased compared with pulse results were still lower than
cell and the accumulated Ah and one programme due to the those of the manufacturer’s
Wh were compared to those cells higher voltage of the pulses. programme.
formed using the manufacturer’s However, it still remained less The last trial to be carried
programme (Table 2). This than that of the manufacturer’s out in this round of testing was
showed slightly more Ah, fewer
Fig 6: Results of pulsed formation programme 1: cell voltage response and temperature
Wh and lower cell temperatures
than the manufacturers
programme, Fig 6, Table 3.
The next step was to reduce
the formation time, keeping
the coulombic input the same.
The pulse programme one was
shortened to 28 hours with the
same Ah input. The current was
increased to compensate for the
fewer operational hours of the
programme. Fig 7 shows the
temperature and battery voltage

Table 3: Formation results tables

Test Programme Total Ah Total Wh Total time h Max temp 0C Water loss cc SG
1 Standard 501 1301 46 51.3 150 1.320
2 Standard 520 1334 46 53.6 190 1.325
3 Pulse 1 316 809 34 39.1 165 1.320
4 Pulse 1 316 1107 34 40.4 171 1.350
5 Pulse 2 384 971 28 54.8 175 1.340
6 Pulse 2 384 960 28 56.6 177 1.320
7 Pulse 3 307 758 22 35.5 98 1.295
8 Pulse 5 327 816 28 59.3 50 1.310

bestmagazine // Spring 2021

48 besttesting
and accuracy of results from
subsequent tests. However,
even at this stage there are
verifiable energy saving results
that have been recorded.
Table 4 shows the results from
these first tests. They list the
formation programmes, the
total or accumulated watt-hours
and ampere-hours, the voltage
response, water loss and the
temperature of the cell during
the process. The formation
Fig 7: Voltage and temperature results from pulsed formation programme 5 programmes are:
• Standard manufacturer’s
to reduce the time to less than and temperature versus time formation, 46 hours
24 hours and reduce the Ah of battery formation. The Ah • Pulsed programme one with
input to an estimated minimum and energy input were nearly same Ah input and reduced
of 5 x C5 capacity. This 5x factor 40% less than those of the time, 34 hours
is not considered as a definitive standard programme value. • Pulsed programme two with
value and will probably need The discharge performance of same Ah input and reduced
to be increased in order to fully the cell was within the range time, 28 hours
form all cells. The reason being of the cells formed by the • Pulsed programme three with
that the normal variation in AM manufacturer’s original, non- lower Ah input and further
weights due to manufacturing pulsing programme. reduced time, 22 hours
tolerances means that cells It is clear from Table 4 that
made with AM weights on the Conclusions the use of pulsing significantly
top end of the tolerance band This is the first set of trials in the reduces energy usage, water loss
will need more Ah to fully convert programme. This stage is not and cell temperature without a
the AM than others produced specifically designed to find a reduction in the formed cell’s
on the minimum tolerance fast energy-saving programme; discharge performance. That is
value. With that said, the results that will come later. It is step one good news. But also significant
were very encouraging. Fig 7 in establishing and validating is the reduction in the time of the
shows the graph of voltage the equipment, methods formation process. The second
reduction of 18 hours, or 40%
Table 4: 14 amp discharge test results summary of the original formation time,
Time to 1.70 Percent of average standard necessitated an increase in the
Programme Adjusted SG
volts (h:m) discharge time 3h:38m pulse current of approximately
Standard 1.295 3h:28m 95 40%. This should have raised the
Standard 1.305 3h:48m 105 cell temperature and increased
the average voltage of the cell,
Pulse 1 1.305 3h:50m 105
compared with the first pulsing
Pulse 1 1.300 3:h49m 105 programme. This it does, but
Pulse 2 1.305 3h:51m 106 with a very small impact on the
Pulse 2 1.300 3h:50m 105 temperature and water loss. This
Pulse 3 1.295 3h:47m 104 is where the pulsing is doing its
job. The voltage dependant gas
Pulse 5 1.310 3h:45m 103
evolution lags slightly behind
Average 1.301 3h:46m 103.6 the voltage rise. Because the

bestmagazine // Spring 2021


current pulse ends after 500ms,
the amount of hydrogen and
oxygen produced is limited to a
brief period before the voltage
drops again and the reaction
ceases due to lack of coulombic
input. This limits the water loss
and also the temperature, as no
heat is generated when there is
no current flowing.
The latest test in this
programme was designed to
reduce the ampere-hour input
to an estimated minimum. It
was designed to ascertain a
boundary limit for a minimum
time and ampere-hour input,
rather than make an attempt
provide a definitive programme.
For this test, the energy use
was more than 40% less than
the initial manufacturer’s
programme and the discharge
result was within the range of
those cells formed using the
manufacturer’s programme. Only
one result has been taken so
far, but will be repeated in the
next round of tests. However,
this result gave the lowest water
loss and energy usage, with
an acceptable discharge time,
within the variation limits of the
previous results.
Summary
The objectives for stage one of
the formation testing programme
have been mostly achieved. The
Digatron unit has been shown
to provide a pulsing power
supply and can accurately record
the accumulated watt-hours
to measure the energy used
in the pulsing programmes.
There is a problem of memory
overload due to the number of
data points collected during a
pulsed programme. This is being
besttesting 49
Because the current pulse
ends after 500ms, the amount
of hydrogen and oxygen
produced is limited to a brief
period before the voltage drops
again and the reaction ceases
due to lack of coulombic input”
addressed in the Digatron’s
battery management software.
There is also an alternative
method of recording the energy
used, via an external source
that will be tested in the next
phase. The results from the
pulsing programmes tested in
this round of the programme
were encouraging. The original
48 hours have been reduced
to 28 for the same Ah input.
The temperature recorded in
this pulsed formation schedule
was lower than that of the
manufacturer’s schedule. This
is despite there being seven
1-hour pauses in the original
programme and none in the 28-
hour one.
The tests demonstrated that
the time and energy used were
considerably reduced with
a pulsed charging algorithm
compared to an analogue
constant-current input. The 22
hour schedule will be repeated
with the same Ah input as
the manufacturer’s schedule
to ascertain if the energy,
temperature and water loss
improvements over the standard
method, recorded in the other
pulsed formation schedules, can
be maintained.
The work will continue to
concentrate on constructing a
22-hour traction programme with
reduced energy and coulombic
input for traction cells, compared
with the 46-hour and first
two pulsing programmes.
The 500ms CC pulse and zero
amp pauses will be carried
into stage two (comparing
manufacturer’s schedules
with new programmes) for
operational and benchmarking
reasons. In addition to the 2V
cells, we will begin trials on 65Ah
12V SLI batteries. This will be a
significant step, as the formation
programmes for SLI batteries
are invariably shorter with a
far lower ratio of ampere-hour
input to rated capacity, when
compared to traction products.
Additionally, a more efficient,
and less memory hungry,
method of recording ampere-
hours and energy input has to be
determined.
Despite these teething
problems, the testing
programme has been
measurably successful in its first
attempt at improving energy
consumption, reducing water
loss and reducing the cell’s
temperature rise during standard
formation procedures. There is
still a lot of work to do. There are
also different formation methods
such as two-shot electrolyte,
filling, recirculating electrolyte
and tank plate formation to
consider. However, going
forward, and based on the
results so far, we can confidently
predict that further advances
and improvements to standard
lead-acid formation schedules
will be reported in the next issue
of BEST.
bestmagazine // Spring 2021