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October 2002 - Features

Additive puts new life in lead acid

Tony Ferreira of Hollingsworth and Vose describes the science and performance of a new paste additive.

The evolution of lead acid battery technology has been driven by the introduction of new materials and new
manufacturing processes and machinery.
The awareness that purity played such a key role in the performance of the battery directed the early battery
technicians to specify ever-purer raw materials. This trend has culminated in the ultra pure requirements for the
manufacture of today's highly performing stationary batteries (Ref.1).
In tandem with the trend for increasing raw material purity, there were great efforts to make more efficient
electrodes, elements and other battery components. The move towards improved battery components was
paralleled with ever improving manufacturing technologies.
Another major strategy used by battery technologists to obtain better battery performance and also to improve the
process of making these devices, has been to use appropriate additives, particularly active material additives.
The role of these additives has been reviewed and it is generally accepted that modern batteries could not function
effectively without their extensive use. (Ref.2).
In this article we shall introduce a new material additive and briefly review its impact on the battery making process,
as well as highlight some key performance advantages.
This new inorganic additive has a noticeable impact on key processes of battery making, namely the mixing of the
pastes that make up the electrode and also the process of making the battery plates. The impact on these process
steps is largely due to the very hydrophilic nature of the new active material additive.
The surface chemical composition of the inorganic active material additive, as well as its geometry and interaction
with the surrounding active material structures, help us understand its impact on battery performance. This impact
is mostly seen on the better charge acceptance and high rate discharge characteristics of the battery.
The impact is universal and it cuts across manufacturing technologies and battery designs. The use of this new
inorganic additive holds much promise for the next round of battery development.

Table 1: Description of NewInorganic Active Material Additive

Chemical Composition: Borosilicate Chemical Grade Glass
Surface Area: >0.3 m2/g
Density: 2.4 to 2.6 g/cc
Average Diameter Range: 0.25 to 10 microns
Length to Diameter Ratio: >5:1
Addition Level: 1% to 3% of Oxide Weight

DESCRIPTION AND USAGE

The new additive is a modified glass microfiber, that is designed and manufactured exclusively for lead acid battery
applications.
The major characteristics of this new active material additive are summarized in Table 1. It is available in industrial
quantities and is shipped in pre-weighed plastic bags. It can be added directly to a paste mixer in much the same
manner that expanders are added in most lead acid battery manufacturing plants. Normal precautions are

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recommended when handling fine particulate, (light facial mask, gloves and appropriate garments).
As one can glean from the above description, this new additive is totally compatible with the electrochemistry of the
lead acid battery. Chemical grade borosilicate glass is extensively used in the lead acid battery in the form of very
absorbent separators that act both as separators and acid reservoirs in one important segment of the valve
regulated type of lead acid battery (Ref.3).
IMPACT ON PROCESS
Preparing a paste batch with the inclusion of this new additive offers interesting possibilities and challenges to the
battery technologist.
As seen in Table 1, the surface of this additive is borosilicate glass. It is well known that water has a zero contact
angle with glass surfaces. This means that there is a very high affinity between the additive surface and water.
Battery paste preparation proceeds by two possible routes:
"Dry Mixing - the oxide and additives are blended dry prior to being wetted by water and sulfuric acid.
"Wet Mixing - water floods the mixer before the addition of the dry ingredients. The acid is added to the wet
oxide mass.
The rheology of paste mixing is complex and has been extensively studied (Ref. 4). In general terms, the amount of
water added to the dry oxide will largely determine the density (cube weight) of the final paste. The other large
contribution to paste density is the addition of sulfuric acid. Sulfuric acid reacts with the oxide to create lead sulfate.
Thus, sulfuric acid impacts paste density by bulking it.

Table 2: Charge Acceptance results of SLI batteries (flooded) and VRLA)

Group: SLI Gr. 31 Flooded Deep Cycle SLI Gr.34 VRLA-Spiral Wound
SAEJ537 (Spec. 22 5A) SAE J537 (Spec.24A) EN50432 (Spec. 9.6A)
Std+/- 39.2A 36.8 A 8.8 A
Std+/HV- 44.8 A (+14)* 43.4 A (+18%) * 11.2 A (+27%)*
HV+/Std- n/a 50 A (36%)* 12.3 A (+40%)*
HV+/- 42.5 A (+8%)* 50 A (+36%)* 10.6 A (+20%)*
* % Difference from control (STD +/-)

Table 3: Cold Cranking results of flooded GR 31 batteries. Average of six batteries

per group.
Group: 750 Amp Discharge 850 Amp Discharge
Volt 30 s Time to 7.2 v Volt 30 s Time to 7.2 v
Std+/- 8.10 v 46 s 7.16 v 33 s
(112%) (153%) (99%) (110%)
Std+/HV- 8.37 v 66 s 7.78 v 48 s

When the paste mix includes the new additive, there will be competition for the water being added. The presence of
the modified glass microfiber impacts the total amount of interstitial water. This means that the battery paste can be
made with a greater amount of water in it and yet retain the required paste density (cube weight). Once this
modified paste is used to paste battery plates, one gets pasted plates with a slightly higher amount of water and
with an additive that is more hydrophilic than the particles of oxide.
The physical model for the interaction of oxide particles and modified glass microfibers can be visualized as a
blending of spheres and rods. The free volume of the packing of spheres is dramatically modified by the presence
of rods (Ref. 5).
When plates containing the modified glass microfiber additive are being made, more of them are produced. These
additional plates are a result of the presence of the additive is four times less dense than lead, and the additional
water used to prepare the modified batch.
Another valuable contribution from the presence of the new additive is the impact the extra moisture has on the
speed of the oxidation reaction that occurs in the first step of curing.

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Beyond the impact on moisture, the presence of this new additive is transparent in the remaining manufacturing
steps. When the additive is present in amounts in excess of 0.5% of oxide weight, it imparts the same mechanical
reinforcement that one encounters with the addition of much larger organic reinforcing fibers.
To summarize, the greatest impact of this new additive to the process of making lead acid batteries is found in the
critical steps of paste preparation and plate pasting. This new active material additive gives the battery technologist
a new tool: the ability to better control the moisture content of paste mixes, plate pasting and curing. Thus, Moisture
Control Management is the single greatest contribution of this new additive to battery manufacturing. This
represents a step forward in the evolution of the process of lead acid battery manufacturing.

Table 4: Cold Cranking results of VRLA Spiral Wound Deep Cycle GR 34 batteries.
Average results of two batteries per group
Group: SAE J537 EN50342
Cold Cranking Cold Cranking
@ 800A @ 800A/480A
10 s Volt= 7.5 s C (Ah)= 9.6Ah
Volt Volt
10 s Time to 7.2 v 10 s C (Ah) to 6.0 v
Std+/- 7.93 v 23 s 7.65 v 8.5 Ah
(105%) (77%) (102%) (89%)
HV+/Std- 8.12 v 31 s 8.15 v 10.6 Ah
(108%) (103%) (113%) (110%)
Std+/HV- 8.01 v 27 s 8.00v 9.2 Ah
(107%) (90%) (106%) (96%)
HV+/- 8.18 v 31 s 7.94 v 9.7 Ah
(109%) (103%) (106%) (101%)

Table 5: Initial Performance values for Gr U1 (35 Ah) 12 v monoblock used in UPS
applications. Average of two batteries of each group.
Group 1 min 5 min 2 hr 5 hr 20 hr
171.4 A 102.3 A 11.7 A 5.5 A 1.8 A
(2.9 Ah) (8.5 Ah) (23.7 Ah) (27.5 Ah) (35 Ah)
HV +/- 6.2 Ah 12.7 Ah 28.2 Ah 31.7 Ah 35.1 Ah
Std+/HV- 6.5 Ah 13.4 Ah 28.7 Ah 32.4 Ah 35.5 Ah
HV +/Std- 5.7 Ah 12.4 Ah 27.5 Ah 31.3 Ah 34.7 Ah
Std +/- 5.3 Ah 11.3 Ah 26.4 Ah 31.1 Ah 35.1 Ah

IMPACT ON SLI BATTERY PERFORMANCE

Since over 60% of all lead acid batteries are destined for the SLI or automotive application, it is natural that this
application should come under scrutiny in the present evaluation study. Thus, both flooded and VRLA battery
designs were selected to participate in the study.
The flooded battery type used was a Gr 31 having a Cold Cranking rating of 750 Amps and a Reserve Capacity of
180 minutes. The batteries tested in this study were made by a well-known manufacturer in the US and are good
representations of the present technology being used to produce flooded automotive batteries.
The automotive VRLA battery selected was the high performance spiral wound design manufactured in Europe.
This battery has been modified to take on deep cycle functions. It was this latter variation that was used in this
study. The spiral wound battery has a Cold Cranking rate of 750 Amps and a Reserve Capacity of 95 minutes.
ENHANCED SLI BATTERY CHARGE ACCEPTANCE
Charge acceptance was tested under two regimes: the SAE J537 and the EN50432 European Standard.
Improvements are significantly higher with the VRLA battery testing.
The improvement in charge acceptance is a key performance enhancement, particularly when this is measured to
be in excess of 25%. This means that the battery can be brought back from a discharged state significantly faster.
Charge acceptance improvements are significantly higher with the VRLA battery testing. Here, the modified plate

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batteries are shown as HV+, when the positives have been modified by the addition of the new additive. HV-
denotes a negative plate modification and HV+/- denotes modification to both plates.
The key observation of these charge acceptance results is that the positive modified group in the VRLA spiral
design batteries gains a significant advantage from the new additive. This is due to its peculiar design as a deep
cycle SLI battery. Overall, when both electrodes are modified, significant improvements occur.
IMPROVED SLI BATTERY COLD CRANKING
Cold cranking is perhaps the most important performance characteristic for SLI batteries. This is a particularly
critical requirement in intemperate climates. The impact on cold cranking by adding the new additive to active
materials is very significant and is reproducible in both flooded and VRLA battery types. It is an enhancement that
is tied to the design of the battery. Therefore, the addition of the new additive will have a greater impact over the
performance of the limiting electrode.
Cold cranking test results are tabulated in Table 3 for flooded Gr 31 batteries. It is clear from these results that this
type of battery greatly benefited from a modification of the negative plates. The improvement in discharge time to
7.2 volts is quite significant (over 50%) when the battery is cranked at its nominal value (750 A), and remains
equally significant when the battery is cranked at the higher current of 850 Amps. Basically, when the negative
plates of this type of battery are modified, the battery easily exceeds the increased cold cranking rate.
The cranking results of the deep cycle version of the spiral wound Gr 34 battery show that the modified positive
plates gained the most from the addition of the new inorganic additive. Here, the gains are in the range of 20% for
the discharge time to 7.2 volts and higher (over 30%) when one examines the cold cranking capacity requirement
of the EN50342 specification.
These results will be explained below in terms of the structural changes to the active materials induced by the
addition of the new additive.

Table 6: BET test results of plates removed from SLI-VRLA gr 34 batteries

Plates Std+ HV + Std - HV -
Unformed 1.66 2.34 2.23 2.58
2 2
m /g m /g m2/g m2/g
% Difference + 40% + 15%
Formed 3.83 4.48 0.55 1.20
2 2 2
m /g m /g m /g m2/g
% Difference + 17% + 118%

IMPACT ON STATIONARY VRLA (AGM) BATTERY PERFORMANCE

Another important step in evaluating the impact of the new additive on the performance of the lead acid battery was
to introduce it in Stationary types. Given the vast array of such batteries, two representative applications were
selected: the Uninterrupted Power Supply (UPS) and the Telecom battery. Both of these applications call for VRLA
batteries using the AGM (Absorbent Glass Mat) technology of electrolyte immobilization. In the present evaluation,
two characteristics are examined: initial performance and deep cycling of the UPS batteries.
The initial performance of UPS batteries shows that the high rates were improved by the addition of the modified
glass microfibers to the plates, particularly the negative plates.
ACTIVE MATERIAL STRUCTURAL CHANGES
The performance chara-cteristics reported in the previous section are due to the structural changes induced to the
active materials of the batteries under investigation, by the addition of the new modified glass microfiber additive.
The investigation tools that are used to look into these structural changes are very widely employed in this field
and, even though additional analytical methods were employed, for the sake of brevity only the most pertinent
results are reported here. Also, given the scope of this work, only selected active materials were tested to explain a
specific effect.
In this manner, BET (Specific Surface Area) analysis of formed and unformed plates is reported here. The results
of this analysis help to explain the impressive high rate results obtained with SLI batteries.
The increased activity of the negative plates is also easier to understand when one examines the results of the X-R
Diffraction analysis of cycled negative plates. The Scanning Electron Microscopy (SEM) technique is used to gain a

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better insight into the changes induced to the active material structures.
BET MEASUREMENTS
The Specific Surface Area of active materials is greatly impacted by the raw materials employed, as well as by the
methods of manufacturing the electrodes (Ref.4). Thus, BET testing, measuring the specific surface area of active
materials, accurately predicts many of the key characteristics of the battery. High rate discharges, in particular, are
highly dependent on high specific surface area values.
Table 6 shows the values of BET measurements done on unformed and formed plates removed from Gr 34 spiral
wound SLI-VRLA batteries. From that table, one can deduce that the impact of the addition of the new additive to
the formed negative active material is quite considerable (118% gain in specific surface area). The gain in the
formed positive is less significant (17%). However, it should be mentioned that the gain in the BET values of the
unformed positive is much greater than the formed positive (about 40%). This result may be a consequence of the
particular requirements of the deep cycle version of this advanced SLI battery design and the radical differences in
the pore structure of the positive and negative plates.
X-RAY DIFFRACTION ANALYSIS
This analytical technique gives us a glimpse into the chemical composition and the crystallography of electrode
surfaces. With this in mind, following a reserve capacity discharge, one battery from each of the four test groups of
Gr 31 flooded SLI batteries was torn down. The plates from the 3rd cell were removed and the negative plates
were washed free of acid and air-dried. The plates were then analyzed for their X-R Diffraction spectra.
In Fig. 3 (overleaf) one sees the spectrum of standard negative plates superimposed on the corresponding XRD
spectrum of modified negative plates. The picture that emerges is that the lead oxide peaks are more intense on
the modified plates and there is a decrease of the pure lead lines in these modified plate spectra. This is an
indication that these plates oxidized more readily than the standard plates when exposed to the oxygen in the
atmosphere.
Because these modified plates contain hydrophilic glass microfiber in their structure and since water catalyses the
oxidation of lead, this finding is not unexpected. It also predicts that modified negative plates would be capable of
having more sites for a more vigorous internal oxygen cycle in VRLA batteries.
SCANNING ELECTRON MICROSCOPY (SEM)
The often-quoted expression that 'a picture is worth a thousand words' is very appropriate when one is with
Scanning Electron Microphotographs. The inner structure of materials reveals itself under power magnifications of
5,000X and 10,000X.
The SEM shown in Fig 4 illustrates the direct comparison at a 2,500X magnification between standard organic
fibers and the new modified glass microfibers. The difference in diameters is at least an order of magnitude
between the two materials. Another interesting observation is the relative amount of each. The larger organic fibers
are few and far between. However, the much more numerous smaller inorganic fibers are every where and form
supporting networks for the active material.
Fig 5 provides a closer look (5,000X and 10,000X) at the interface between the special inorganic microfibers and
the surrounding active material. It is obvious that around each microfiber one finds a micro gap that will fill up with
electrolyte when the electrode is wetted. The very surface of the glass microfiber is equally covered in active
material particulate. This intimate contact between the modified glass microfibers, and the possibility that they
provide micro gaps that allow electrolyte to have easy access to the active material during intense utilization
periods, explain the enhanced performance of the limiting electrodes during high rate discharges.
The SEM is also a powerful tool to analyze the underlying structures of the negative active material. Using
well-known techniques (Ref.5), the NAM of cycled Gr 31 plates that had been subjected to the XRD analysis were
also treated to reveal their skeleton structure.
Fig. 6 A & B show the difference between the skeleton structure of standard and modified negative plates. The
modified negative NAM appears to be much more open with a very large surface area crystal formation.
The three analytical techniques used, illustrate the structural changes that are induced by the presence of modified
glass microfibers in active material with the inner specific surface area as measured by BET greatly increased.
XRD shows that the surface of negative plates is easier to oxidize, explaining the higher capacity to enhance the
oxygen internal cycle. SEM views of the active materials also provide a glimpse of how these special microfibers
interact with the active materials, create a network of micro gaps through which the electrolyte has easier access to

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the active material.

Since all electrochemical reactions rely on fast ion transport, and given the observation that the new microfiber
additive impacts the active material structure to facilitate electrolyte penetration, this new additive can be known as
an ION FLOW ENHANCING ADDITIVE.
(1)F. Fleming, 'Float Life Verification of a VRLA Battery Utilizing a High Purity Electrochemical System', Intelec
1999, Section 3-3
(2)A. Ferreira, J. Power Sources, 95 (2001) 255-263
(3)G. Zguris, J. Power Sources, 67 (1997) 307-313
(4)H. Bode, Lead-Acid Batteries, John Wiley, New York, 1977
(5)D. Pavlov, J. Power Sources, 7 (1981/82) 153-164battery science

All material subject to strictly enforced copyright laws. © 2005 Euromoney Institutional Investor PLC.

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