4.

0 Separators
A separator is a material that is inserted between the positive and negative plates of the
cell to prevent short circuiting. The development of separators was essential to the growth
of the lead-acid battery industry. They have gone through many changes during their
history. The earliest designs of lead-acid battery employed materials such as porous pot,
flannel and felt to separate the plates. In the 1880s, perforated hard rubber, India rubber,
sponge and cork were used as separators. The first use of wood separators was in 1892 by
E.P. Usher and by G.H. Roe and G. Sutro. Wood was the separator of choice for many
years. It began to be phased out in favor of rubber, cellulose and PVC separators as
recently as the 1940s and 1950s.

The separators used today in lead-acid batteries reveal a great deal of variation in
materials, design and in how they are used in the battery assembly. They can be made
from plastic, rubber, glass fiber, cellulose and sulfuric acid gel. Today, most separators
for flooded types of automotive and industrial batteries are made from microporous
polyethylene, while in valve-regulated batteries, absorptive glass mats or sulfuric acid
gels are employed. While separators in flooded types of batteries act as a physical barrier
between the plates, the separators in valve-regulated batteries perform an additional
function acting as a medium for transport of oxygen from the positive to the negative
plate.

Separators for flooded batteries have a standardized design a backweb on which ribs are
formed. The backweb prevents the plates from touching, while the ribs form channels
that contain the electrolyte and allow escape of gas from between the plates. A wide
variety of backweb thicknesses and rib configurations are used by the battery industry,
depending on the desired properties of the separator and the battery. A typical profile for
an automotive battery separator is shown in Figure 4-1. Industrial battery separators have
a considerably thicker backweb for longer life and taller ribs to increase the amount of
electrolyte between the plates.

Figure 4-1: Typical profile of microporous polyethylene automotive battery separator

The most common separators for flooded batteries are produced from polyethylene,
polyvinyl chloride, phenolic resins and natural rubber. Polyethylene separators are
produced from a mixture of high-molecular-weight polyethylene, silica and oil which is
extruded into a sheet at high temperature. Ribs are then added by passing the sheet
through calender rollers. Some of the oil is then extracted with organic solvents, leaving
about 10%-20% remaining in the separator to improve its flexibility and oxidation
resistance. The flexibility of microporous polyethylene separators provides a very
desirable mechanical advantage. It allows them to be formed into sleeves and pockets for
improved isolation of the plates.

Polyvinyl chloride separators are manufactured from a mixture of powdered PVC, silica,
water and a solvent. This is extruded at an elevated temperature and calendered to
provide the required number and design of ribs. The solvent is extracted in hot water.
After drying, a rigid, porous sheet results.

Rubber separators are produced from a blend of rubber, silica and water. These
components are blended in a mixer, extruded into a sheet and calendered to form the ribs.
The extruded sheet is then vulcanized to produce a hard, rigid sheet. Curing can also be
done by cross-linking with an electron beam, producing a more flexible product.

Phenolic separators are produced by blending silica with phenolic resin and then forming
this mixture into a sheet on a polyester scrim. Ribs are then extruded onto the resin sheet
in a separate operation.

Although separators perform an essential function in ensuring long life, they reduce the
capacity and high-rate performance of batteries. This is because they displace electrolyte
and add electrical resistance. To reduce these losses, separator manufacturers are
constantly working to increase the porosity and reduce the electrical resistance of their
products without sacrificing mechanical strength.

The specific properties common to all separators are:

• Low acid solubility

• Good oxidation resistance
• Low electrical resistance
• Low acid displacement
• High tensile strength
• Good flexibility
• High porosity
• Good wettability
• Low level of leachable impurities.

4.1 Life
Low acid solubility and oxidation resistance are important to ensure that the separator is
capable of functioning over the life of the battery. Battery separators are subjected to both
physical and chemical degradation in service. Significant increases in temperature,
electrolyte concentration, overcharge and service conditions can accelerate the
degradation to some degree. The failure mode is very dependent on the material used to
make the separator and the type of battery service. The rate at which the separator
degrades in the battery depends on the thickness of the backweb and, in the case of
microporous polyethylene separators, on the amount of residual oil. Increasing the
amount of oil in the separator improves its oxidation resistance, but if the oil content is
too high, it can leach out of the separator and cause problems, such as blocking of the
vent caps. There is no industry standard test for physical and chemical degradation of
separators, but the following tests are in use by battery and separator manufacturing
companies:

• sulfuric acid/dichromate oxidation

• sulfuric acid/hydrogen peroxide oxidation
• overcharge oxidation.

4.2 Electrical Resistance

Electrical resistance of the separator is a measure of its ability to transfer ions from one
electrode to the other. This has a direct effect on the performance of the battery by
increasing the internal resistance of the cells. The major contributor to resistance is the
backweb and, to a lesser extent, the resistance of the ribs. The resistance of the separator
can be expressed as:

Rsep =Rel (t2/p-1)

Where: Rsep = separator resistance (Ω cm)

Rel = electrolyte resistance (Ω cm)

T = tortuosity = l/d

P = porosity

Figure 4-2 shows the relationship between backweb thickness and electrical resistance
for a typical automotive battery separator. The graph shows that for every 0.001 inch
increase in backweb thickness, the electrical resistance increases by approximately 7%.
Clearly, separators for batteries designed to operate at high discharge rates must have a
thin backweb. However, for industrial batteries which are discharged at much lower rates,
a thicker backweb can be employed.

Figure 4-2: Electrical resistance of battery separators

4.3 Acid Displacement
Acid displacement results from separators taking up space that could be utilized for
additional electrolyte. The amount of acid displaced is the volume of the solid fraction of
the separator and can be calculated from:

D = (Vb + Vr) (1-P)

Where: Vb = volume of backweb

Vr = volume of ribs

P = porosity

For an automotive battery separator with a 0.008-inch backweb, the acid displacement
will be around 95 ml/m2. If the backweb is reduced to 0.006 inch, the acid displacement
will be reduced to 80 ml/m2. This provides additional electrolyte to participate in the cell
reaction, which increases the capacity. Alternatively, the plates can be spaced closer
together while still retaining the same electrolyte volume. This will improve the high-rate
performance of the battery. Ideally, the backweb thickness should be as low as possible.
However, consideration has to be given to the strength and durability of the separator.
This results in a trade-off between performance, strength and life. As a general rule,
separators for automotive batteries will have a backweb in the 0.008-0.010 inch range
while a backweb of 0.030-0.040 inch is common in industrial batteries.

4.4 Porosity
Porosity is that fraction of the separator volume that is composed of voids that are
capable of holding sulfuric acid. The greater the porosity, the greater is the amount of
electrolyte that can be retained in the separator and, for a given thickness, the lower the
electrical resistance. Not all the pores in a separator are filled with electrolyte. Some are
totally enclosed by the separator material. Some are also dead ended, preventing ions
from being transported between the electrodes. The pores can be thought of as storage
areas holding the inventory of sulfuric acid that participates in the electrochemical
reaction. Ideally, the higher the porosity, the better. However, once again, there is a trade-
off between the ideal and serviceability.

4.5 Strength
Strength of separators encompasses a number of factors including stiffness, puncture
resistance, rigidity, flexibility, brittleness and tensile strength. These factors become most
important during assembly, when damage can lead to short circuits in the battery. The use
of expanded metal grids with exposed sharp protrusions requires separators that have
high puncture resistance, while flexibility is essential for enveloping or sleeving the
plates. High tensile strength and flexibility are required for separators that are to be used
with automatic wrapping/stacking machines. At the end of the 20th century, automotive
batteries were almost exclusively built with enveloped plates that require high flexibility
and tensile strength. Therefore, microporous polyethylene separators are by far the most
widely used.

4.6 Flexibility
Flexibility can be increased by reducing backweb thickness. However, this leads to
reduced stiffness, which can result in problems during assembly. The loss in stiffness in
the direction of the ribs is only minor, but is significantly more serious in the cross-rib
direction. A reduction in backweb thickness from 0.008-0.006 inches results in a
reduction in stiffness of only 2% in the rib direction, but a reduction of 60% in the cross-
rib direction (W. Böhnstedt, Journal of Power Sources, 67 (1997) pp. 299-305). A loss of
stiffness results in a loss in accuracy of cutting and folding during production of separator
pockets. To reduce this problem, separator profiles have been developed with cross ribs
that have a considerably lower profile to avoid hindering the release of gas from between
the electrodes. With suitable design, cross ribs can compensate for loss in stiffness
without significantly affecting the electrical resistance and acid displacement.

4.7 Puncture Resistance

Puncture resistance also depends on backweb thickness. This relationship is shown in
Figure 4-3. The puncture resistance can be increased by increasing the ratio of polymer
to filler in the material. This, however, increases the cost, reduces the porosity and
increases the electrical resistance. The puncture resistance can also be increased by the
use of polymers of higher molecular weight, but breakdown of the polymer chains during
processing limits the benefits that can be obtained.

Figure 4-3: Puncture resistance of battery separators as a function of backweb thickness

Industrial battery separators are considerably thicker than those for automotive batteries
and are available in a wider choice of materials. In addition, glass mats are often attached
to the ribs to reinforce the active material and to prevent it from expanding into the space
between the rib and backweb. On the following page in Table 4-1 is a summary of
separator properties, as shown in G.H. Brilmyers Journal of Power Sources, 78 (1999)
pp. 68-72.
Separator Type Hard Flexible Phenolic
Rubber Rubber Resin
Polyethylene PVC
Strength Excellent Good Good Fair Good
Rigidity/flexibility/brittleness Flexible Rigid Rigid Flexible Rigid
Mean pore diameter (µm) 0.10 0.22 0.20 0.06 0.50
Volumetric porosity (%) 55-65 60-70 50-60 45-55 60-70
Water permeability 0.045 0.13 0.031 0.020 0.049
(cc/psi/cm2/min)
Backweb thickness (mm) 0.65 0.60 0.70 0.35 0.60
Maximum thickness (mm) 3.5 4.2 5.8 4.1 3.6
Electrical resistance (Ωcm2) 0.120 0.130 0.280 0.250 0.140
Oxidation resistance Excellent Excellent Very good Good Good
Resistance to Sb transfer No No Yes Yes No
Thermal resistance Good Good Excellent Good Good
Rib styles V/D/S V/D V/S V/S V/S
Glass mat Available Available Available Available Available

Table 4-1: Selected properties of lead-acid battery separators V = vertical; D = diagonal; S =

serpentine

4.8 Glass Mat Separators

Glass mat separators are essentially used for valve-regulated lead-acid batteries. These
batteries owe their existence to the discovery that if oxygen formed during charging of
the positive electrode can be transported to the negative plate, it will be reduced and
consequently depolarize the negative plate, thereby preventing hydrogen evolution. No
electrolysis of water takes place and water consumption is eliminated. Although it had
been known for many years that oxygen that diffused through the electrolyte in flooded
cells was reduced at the negative plate, this took place at a very low rate. Milner (P.C.
Milner, The Bell System Technical Journal, 49, 7, pp. 1321-1334 (1970)) calculated that
the rate of oxygen reduction in a typical standby power cell was 20-35 µA per Ampere-
hour of cell capacity. In their groundbreaking patent, McClelland and Devitt showed that
oxygen could be transferred from the positive to the negative plate through a glass mat
that had been partially saturated with electrolyte so that unfilled channels were available
for oxygen transport (D.H. McClelland and J.L. Devitt, U.S. Patent 3,862,861 (1992)).
Today, microfiber glass mats are the most common separators used in valve-regulated
lead-acid batteries. Like the separators used in flooded systems, they keep the plates
separated, but also have the ability to allow oxygen transport from the positive to the
negative plate.

The glass fiber mats used in valve-regulated batteries have a porosity greater than 90%
and a surface area exceeding 1 m2/g. The large surface area is achieved by use of glass
fibers having a very low diameter, around 1 micron. Glass fiber has a zero contact angle
with sulfuric acid; therefore, the separators have high capillary forces which result in
good wettability. They are compressible and conformable so that they provide support for
the electrodes. They are usually made from blends of glass fibers of different diameter
that are processed into mats on paper-making machines. Fibers below 1 µm give a large
surface area and a well dispersed structure of small channels for acid absorption and
oxygen transport. But, due to their shortness, they give little tensile strength to the mat.
Fibers having a larger diameter improve strength, but are also more brittle and increase
the tendency to break when compressed. A typical composition will have a ratio of 20%-
30% microfine fibers. This gives an acceptable balance between electrical properties,
strength and cost. A simplified view of the glass-fiber-separator structure is shown in
Figure 4-4 Typical properties of glass mat separators for valve-regulated batteries are
shown in Table 4-2. (W. Böhnstedt, Journal of Power Sources, 78 (1999) pp. 35-40).

Figure 4-4: Simplified view of glass microfiber separator structure

Basic weight (g/m2) 200

Porosity (%) 93-
95
Mean pore size (µm) 5-10
Thickness (acid filled) at 10 kPa (mm) 1.3
at 35 kPa (mm) 1.0
Puncture strength (N) 7.5

Table 4-2: Typical properties of glass fiber separators for valve-regulated lead-acid
batteries

The strong capillary forces in glass mat separators result in good wicking characteristics.
Figure 4-5 shows how the percentage of fibers (<1µm) affects the rate of wicking.

Figure 4-5: Effect of fiber mix on wicking characteristics of glass mat separators
The time for the electrolyte to wick to a given height decreases as the percentage of fine
fibers in the mat is increased. All voids do not fill uniformly. However, the smaller voids
will fill preferentially and the larger voids more slowly. The result is a larger proportion
of unfilled large voids in the upper part of the separator. This is the area where the
greatest amount of oxygen transfer takes place.

Acid stratification can take place in valve-regulated batteries with glass mat separators
just as it does in flooded cells. And for the same reason sulfuric acid formed during
charging will diffuse downward and displace acid of lower concentration to the top of the
cell. Stratification is difficult to avoid in glass mat separators since the electrolyte is
never stirred by the bubbling action of oxygen and hydrogen when the battery is charged.
Figure 4-6 shows how the height of the plates in a valve-regulated battery affects the
stratification and the capacity (R.E. Nelson, private communication).

Figure 4-6: Stratification effects with glass mat separators

A viable strategy for reducing stratification in a valve-regulated battery is to turn the

battery on its side, which reduces the wicking height. No leakage takes place because the
cells contain no free electrolyte. Figure 4-7 shows how the orientation of the battery
affects the capacity of valve-regulated cells during cycling. The graph shows that better
retention of capacity is achieved when the cells are oriented on their side. The best result
is obtained when the cells are positioned with the shortest side in the vertical orientation.
For this reason, many valve-regulated cell installations position the cells on their sides.

Figure 4-7: The effect of orientation on the capacity of valve-regulated cells during
cycling

Among the most important attributes of glass mat separators are compressibility and
conformability. Conformability allows the separator to adapt to imperfections in the
battery plate and maintain good plate-to-electrolyte contact. When the battery is
discharged and charged, the plates will expand and contract. Conformability allows the
separator to accommodate these changes without losing contact with the plate.

Recent studies have shown that high levels of compression can improve the cycle life of
valve-regulated batteries. The glass fibers essentially act like springs between the battery
plates and support the active materials. The support can be increased by using separators
with higher density and by using a greater percentage of fine fibers in the glass blend. A
two-gram sample of fine fiber (diameter 0.8 µm) has approximately 5.6 billion fibers,
while a coarse fiber (diameter 3.5 µm) has only 28 million fibers.

The degree to which the separator is compressed is an important factor in the design of
the battery. The optimum amount of compression has not been determined. It is affected
by the type and thickness of the separator and the plate spacing. It is known, however,
that too little compression will result in premature battery failure, while too much will
compress the spongy lead in the negative plate. The compression is reduced when the cell
is filled with electrolyte. Therefore, the compression remaining after filling is the critical
value. For example, Zguris (Journal of Power Sources, 67 (1997) pp. 307-313) has
reported that the force required to compress a stack of glass mat separators wetted with
sulfuric acid of 1.23 specific gravity to a 46% compression was reduced to 60% of the
value required to compress the dry material. The amount of compression will affect:

• porosity of the separator

• volume of electrolyte
• time to fill
• container wall strength
• shock and vibration requirements.

The ability of the separator to act as a spring is affected by the amount of compression.
There is a permanent loss in thickness when the glass mat is compressed. Figure 4-8
shows the effect of different compressive loads on the thickness of the separator
compared to when the load is removed. The data shows that a loss in thickness takes
place that is proportional to the amount of compression applied.

Figure 4-8: The effect of compressive force on the thickness of glass-mat separator
material

The issue of compression in glass mat separators still requires further work. Clearly,
compression has an important effect on the performance and life of the battery. If the
compression is too low, battery life will be compromised. If it is too high, compaction of
the negative plate will take place, filling will be difficult and the amount of electrolyte
will be reduced. In this case, the capacity of the battery will be reduced. The level of
compression should take into account the design of the battery, the characteristics of the
separator and the degree of saturation desired.
4.9 Gelled Electrolyte
Gelled electrolyte provides an alternative for the valve-regulated battery. As pointed out
previously, there are still some unresolved problems with glass mat separators in valve-
regulated batteries. Consequently, many valve-regulated batteries use an electrolyte that
is immobilized by gelling. The most common gel is formed by the addition of between
5%-8% of silica to the electrolyte. These gels are thixotropic and can be fluidized by
mechanical stirring. They can be added to the cell in liquid form and then allowed to gel
after the required amount has been added. Initially, the gel provides an impermeable
barrier to oxygen transfer, preventing any gas recombination. Overcharge results in water
loss which causes the gel to shrink and develop cracks. This enables oxygen to migrate to
the negative electrode and be reduced. Once the oxygen cycle has been established, no
further water loss takes place. (O. Jache, German Patent 1,671,693 (1967.)) A conceptual
view of the recombination process with gelled electrolyte is shown in Figure 4-9.

Figure 4-9: Conceptual view of the recombination process with gelled electrolyte

Batteries that use gelled electrolyte also use a conventional separator to prevent short
circuits and to control the spacing between the electrodes. It is important that these have
minimal acid displacement. The combination of the standard microporous separator and
gel results in reduced electrolyte volume. Typical data for microporous separators
suitable for use in gelled electrolyte valve-regulated batteries are shown in Table 4-3 (W.
Böhnstedt, Journal of Power Sources, 78 (1999) pp. 35-40).

Backweb thickness (mm) 0.3

Porosity (%) 70
Mean Pore Size (µm) 0.5
Acid displacement (ml/m2) 14
5
2
Electrical resistance (mς cm ) 12
0

Table 4-3: Typical properties of microporous separators for valve-regulated batteries with
gelled electrolyte