0 Electrode Materials

Although a number of basic materials are used to produce all types of lead-acid batteries,
significant differences exist among battery types in both materials and design. Batteries
are built to satisfy specific application-based demands. Each particular duty cycle
prescribes its own design, materials and methods of construction. For example, engine-
starting batteries use lead-calcium alloys for their high conductivity needed for high
cranking rates. Motive-power batteries use lead-antimony alloys for their renowned
cycling capability. Different separator and container materials meet the needs of a wide
variety of performance life and environmental conditions.

2.1 Lead
Lead is the basic raw material used to produce the lead oxide and alloys used to make
lead-acid batteries. The industry standard for pig lead is ASTM Designation B29-79(84),
which covers two grades used to produce oxide for active material or for mixing with
other elements to produce alloys. The specifications are shown in

Table 2-1.

Element Corroding Lead % Impurities Common Lead % Impurities

Silver 0.0015 0.005
Copper 0.0015 0.0015
Silver/Copper (combined) 0.0025 ---
Antimony, Arsenic, Tin
0.002 0.002
(combined, maximum)
Zinc (maximum) 0.001 0.001
Iron (maximum) 0.002 0.002
Bismuth (maximum) 0.050 0.050
Lead (by difference) 99.94 99.94

Table 2-1: Chemical requirements for ASTM designation B29-79(84)

The only difference between these designations is the permissible concentrations of silver
and the aggregate of silver and copper. Both elements increase evolution of hydrogen
from the negative electrode. Therefore, corroding lead or lead of even greater purity is
generally used in battery types where low water loss is required.
Most battery manufacturers use their own specifications and can specify lower limits and
additional elements not included in Table 2-1. The Battery Council International (BCI)
has also developed specifications for Standard Reference Materials used by lead-acid
battery manufacturers. They include antimony alloys and calcium alloys with and without
tin. They are shown in Table 2-2.

Antimony %
Element in Alloy Calcium-
Element Calcium
1% 3% 6%
Tin
Aluminum <0.0005 <0.0005 <0.0005 0.019 0.018
Antimony 1.08 2.70 5.98 <0.0003 <0.001
Arsenic 0.136 0.151 0.169 <0.0003 <0.0005
Bismuth 0.0103 0.0073 0.0046 0.0105 0.010
Calcium <0.0005 <0.0005 <0.0005 0.111 0.085
Copper 0.0107 0.053 0.057 0.0003 0.0004
Iron <0.0003 <0.0003 <0.0003 <0.0003 <0.0005
Nickel 0.0003 0.0004 0.0004 <0.0002 <0.0002
Selenium 0.0142 <0.0005 <0.0005 <0.0002 <0.0001
Silver 0.0018 0.0012 0.0010 0.0017 0.0017
Sulfur 0.0015 0.0037 0.0037 <0.0005 <0.0005
Tin 0.19 0.165 0.306 <0.001 0.272
Tellurium <0.001 <0.001 <0.002 <0.0003 <0.0001
Zinc<0.0003 <0.0003 <0.0003 <0.0003 <0.0005 <0.0003

Table 2-2: Chemical analyses of BCI standard reference materials

The BCI standards provide general guidance to the industry. However, as in the case for
lead metal, battery manufacturers frequently use their own specifications for alloys.
Standards have also been developed for battery containers and separators.

2.2 Lead Oxides as Starting Material

Lead oxides have been used in lead-acid batteries as starting materials for plates since the
early days, particularly lead monoxide (PbO) and red lead (Pb3O4). It was customary to
use a mixture of lead monoxide and red lead in the positive plates and pure lead
monoxide in the negative plates. In contrast to today, these oxides contained very little
free lead, as most battery producers then believed that it lowered the quality of the
product.
The development of two processes, Ball Mill and Barton, for oxide production resulted in
a dramatic change in the oxides used for battery manufacture. Both processes
considerably reduced the cost of lead monoxide, but yielded a material containing a
significant amount of free lead. The material is generally called leady oxide. Prompted by
the reduced cost, battery companies developed paste formulations and new processes, i.e.,
curing, that permitted leady oxide use. Starting in the 1930s, leady oxide became the
material of choice. Its principle advantages are:

• low production cost

• usable for both positive and negative electrodes
• usable for all types of lead-acid batteries.

Some disadvantages of leady oxide exist, for instance, no batch-to-batch exact

repeatability in the manufacturing process. This causes variability in the preparation of
pastes and thereby variability in plates. Free lead remains in the plates following pasting
and subsequently has to be removed during the curing process. This extends the curing
time, increases the inventory of plates and, perhaps most seriously, prevents development
of continuous paste mixing-pasting-drying-assembly processes.

With the advent of valve-regulated batteries and battery applications that demand a high
degree of reproducibility among cells, non-leady oxides, particularly pure lead monoxide
and red lead, have had an upsurge in use. These materials can be made to exact chemical
compositions, eliminating most of the variability associated with leady oxide. They also
reduce curing time and allow continuous plate-making technology. In addition, red lead
reduces formation time and improves initial capacity.

An intriguing development of the late 1990s was the use of basic lead sulfates or partially
sulfated oxides to make plates. These materials have the same benefits as non-leady
oxides and also reduce the amount of heat developed when the cells are filled with
electrolyte. The need for cooling is thereby reduced, as is the time between filling with
electrolyte and placing on formation.

Leady oxide still remains the most widely used active material for battery plate
production. The Barton and Ball Mill processes are still used to make leady oxide.

Barton processing begins with feeding molten lead and air into a large pot equipped with
a rotating paddle to agitate the lead. Represented by the equation Pb + ½O2 → PbO, the
formed lead oxide is drawn off by an air stream, classified with a cyclone and blown to a
hopper. Often, it is also passed through attrition mills to produce different particle size
distributions for different battery applications.
Varying the conditions under which the reactor operates permits controlling the degree of
lead oxidation, particle size distribution and the ratio of αPbO to βPbO in the product. For
example, high-temperature-reactor operation reduces the amount of free lead in the oxide
and increases the amount of βPbO. By reducing temperature, free lead is increased, as is
the ratio of αPbO to βPbO. Air-flow rate through the reactor also affects characteristics of
the oxide. Increased air flow increases both free lead and oxide particle size as shown in
Table 2-3. Conversely, decreasing air flow reduces both free lead content and particle
size. The Barton system is extremely versatile, which is why it is so widely used by the
battery industry as shown in Table 2-4.

Attrition mill oxide, also leady oxide, is more commonly produced in Europe and Asia.
Barton oxide is more common in the United States. In the attrition mill process, lead balls
or ingots are tumbled in a rotating drum. The lead is abraded through friction and
oxidized by air passed through the drum. The oxide produced this way is generally finer
than Barton oxide. It has a greater acid absorption value, usually in the range of 220-240
mg/g. The oxide contains no β modification, since the temperature of the reaction in the
attrition mill is only about 100ºC.

Apparen Acid
Particle
t
Absorptio
Size Output
Free Lead Density n
Air Flow Higher Higher Higher Lower Coarser Higher
Lower Lower Lower Higher Finer Lower
Temperatur
Higher Lower Lower No effect No effect Higher
e
Lower Higher Higher No effect No effect Lower

Table 2-3: Variable conditions and effects in the Barton process

Characteristic Automotive Batteries Industrial Batteries

Free Lead (% by weight) 18-24 22-28
3
Apparent Density (g/in. ) 18-24 23-29
Acid Absorption (mg/g) 170-210 130-155
Particle Size: Median (μm) 3.0 3.5

% below 1 μm 10-15 5-10

Alpha: Beta Ratio 96:4 96:4

Table 2-4: Barton process leady oxide characteristics for different battery applications
most important to battery manufacturers
2.3 Pure Lead Monoxide
Pure lead monoxide is becoming widely used by battery manufacturers, particularly of
valve-regulated batteries. The most important way it differs from leady oxide is its
absence of free lead. Particle size is greater and acid absorption lower than required for
automotive batteries, but is about equivalent to the leady oxide used in industrial
batteries. The absence of free lead improves the reproducibility of paste mixing and
curing. As noted above, with leady oxide some free lead is oxidized during paste mixing
and more oxidation occurs during pasting and curing. Since the amount of oxidation is
variable in each step, inconsistent paste characteristics result; therefore, there is reduced
reproducibility in the finished plates. The result is further variability in the cells made of
these plates. This is a major problem in valve-regulated batteries where cell-to-cell
voltage repeatability is important for proper long-term operation under oxygen
recombination conditions. Another advantage of lead monoxide is that no lead-oxidation-
elimination step is required in the curing process. This reduces time and permits design of
process conditions for producing the optimum ratio of tribasic and tetrabasic lead sulfates
in the plates.

Characteristic Value
Free Lead (% by weight) 0.10
Apparent Density (g/in.3) 26-32
Acid Absorption (mg/g) 125-
150
Particle Size: Median (μm) 4.5

%<2 μm 20

%<1 μm 5
βPb0 (% by weight 90

Table 2-5: Typical characteristics of battery grade lead monoxide

2.4 Red Lead

Red lead is beneficial in improving the electrochemical performance of lead-acid
batteries. The lead is in a higher oxidation state, at a ratio of lead:oxygen = 1.33, than in
lead monoxide and its electrical conductivity is also higher. Batteries made with red lead
in the positive paste can be formed quicker. They also have an initial capacity higher than
those made from leady oxide pastes.

Red lead is normally used in one of two ways: a high-percentage red lead (~80% % by
weight Pb3O4) can be blended into a paste mixture to produce the desired amount in the
finished paste, or a lower-percentage red lead (~25% % by weight Pb3O4) can be
substituted for leady oxide. Either way, paste-mixing and plate-pasting processes are very
similar to those with leady oxide. Particle size decreases and acid absorption increases as
the percentage of Pb3O4 in the red lead is increased. Thus, if a paste mix is produced
containing 25% by weight Pb3O4, a better result is generally obtained when it is added as
the higher percentage material due to its higher reactivity.

Characteristic 25% by Weight Red Lead 80% by Weight Red Lead

% by weight Pβ3O4 25±3 80 ±3
% by weight PβO 75 ±3 20 ±3
% by weight Pβ 2.5 max. 0.5 max.
3
Apparent Density (g/in. ) 19-25 16-19
Acid Absorption (mg/g) 170-200 200-230
Median Particle Size (μm) 3.0 2.0

Table 2-6: Typical characteristics for battery-grade red lead

2.5 Oxide Production Methods

Oxide production methods for leady oxide, Pb0 and red lead are illustrated in Figure 2-1.
Due to its low cost and flexibility, most lead oxide in the United States is produced by the
Barton process. Barton pot oxide is also used as the feedstock for producing pure lead
monoxide (Pb0) and red lead.

As shown in Figure 2-1, lead of the required purity is melted in a kettle and then fed into
a reactor vessel equipped with a rotating paddle. Air is drawn through the reactor and
leady oxide is drawn off by the air stream and classified by conventional methods. By
careful control of temperature, air flow and paddle speed, oxide of various characteristics
can be produced. Generally, the temperature will influence the amount of free lead and
the alpha:beta ratio in the oxide. The velocity of the air flow will influence the amount of
free lead and particle size of the material.

Pure Pb0 and red lead are produced in calcining furnaces, in which the raw material is
agitated while being heated at the optimum temperature for oxidation to the required
product. For Pb0, the temperature is held at 600ºC. For red lead, a temperature of 450ºC to
500ºC is used. For red lead, the furnace is discharged when the desired amount of Pb3O4
is reached. Oxide with 25% by weight red lead can be made in 5-6 hours, while an oxide
with >80% Pb3O4 may require 16-18 hours of calcining.

The most important physical property of the oxide is particle size distribution,
influencing both battery performance and life. Though the Barton process is capable of a
great degree of flexibility through process parameter adjustments, a system with a
hammer mill provides greater control of particle size. In a hammer mill, a variable-speed
rotating shaft is fitted with a number of hammers. An air stream is drawn through the mill
and controlled by a damper setting. Oxide dwell time in the mill can be varied depending
on air velocity, while the amount of grinding is controlled by the number of hammers and
rotation speed. The oxide being fed to the mill can be ground to a wide range of particle
size distributions. Process settings have been established that allow a high degree of
control over median particle size and amount of fine particle in the product. Through a
combination of equipment and process, oxide particle size distribution can meet the
desired specifications of the battery manufacturer.

Figure 2-1: Schematic diagram of process for production of leady oxide, lead monoxide
and red lead

2.6 Lead Sulfates as Starting Material

Other active materials than lead oxides are used by some battery manufacturers as the
starting material for the active mass. In the late 1990s, battery designs included electrodes
wound into a spiral. These batteries have a very high plate-surface area, resulting in
delivery of very high power output. A problem with this type of construction is the
heating that occurs when cells are filled with electrolyte. A reaction between sulfuric acid
and unreacted oxide in the paste results. The manufacturer may need to install cooling
systems to remove the heat before the battery is formed. In extreme cases, the reaction is
so rapid that the specific gravity of the electrolyte drops to a dangerously low level,
leading to dissolution of the lead sulfate. When the cells are placed on formation and the
specific gravity of the electrolyte again rises, the lead sulfate can precipitate in the
separator and short circuit the cell.

The problem can be reduced or eliminated by use of pastes composed of lead sulfate and
water. Depending on battery application, tribasic lead sulfate, tetrabasic lead sulfate or a
mixture can be used. The paste can be made from pure lead sulfates or oxide sulfated to a
higher than usual degree. Cells made with highly sulfated plates evolve less heat when
they are filled with electrolyte and do not require cooling. Short circuiting problems are
also eliminated.

2.7 Sulfuric Acid

Sulfuric Acid plays a dual role in a lead-acid battery, both as a reactant and an electrolyte,
i.e., an ionic conductor. It is important that the acid used in the electrolyte is pure and
does not contain any impurities that can affect battery performance. The battery industry
considers sulfuric acid that meets Federal Specification O-S-801-b to be acceptable for
electrolyte manufacture. The impurity limits in Federal Specification O-S-801-b are
shown in Table 2-7.
 Impurity Maximum Allowed (%)
Organic Matter 0.0
Non-Volatile Matter 0.0250
Alumina 0.0006
Iron 0.0050
Arsenic 0.0001
Antimony 0.0001
Calcium Oxide 0.0006
Chromium 0.0001
Copper 0.0001
Lead 0.0001
Manganese 0.00005
Nickel 0.0001
Platinum 0.00001
Selenium 0.0001
Tellurium 0.00005
Chloride 0.0010
Nitrate and Nitrite 0.0010

Table 2-7: Maximum impurity limits for sulfuric acid in lead-acid battery electrolyte

The concentration of sulfuric acid that is used in the various processes for production of
lead-acid batteries can span a wide range. Thus, it is usually purchased as 93.19% H2SO4
(1.835 s.g.) and then diluted to the required strength for either the process or the battery
type.

2.8 Grids
For the majority of lead-acid batteries, the positive electrode controls performance and
life. Battery failures are generally caused by degradation of the positive plate. Based on
surveys of failed automobile batteries, the predominant causes of failure have been:

• grid corrosion
• grid growth
• active material shedding.

In the late 1990s, some negative-plate-based battery failure has been identified in valve-
regulated batteries in float service. Though not fully understood, the phenomenons most
likely cause relates to self-discharge resulting from insufficient polarization while
charging.

As noted above, positive plates have to meet different missions depending on battery
application. This has resulted in considerable differences among the materials, design and
processing of these plates for automotive, industrial and standby applications.

Positive grids in all batteries act as both support structure and electrical conductor. They
must be capable of withstanding all handling operations during production, such as
casting, trimming, pasting, stacking and welding. They must also have adequate electrical
conductivity to reduce Ohmic losses during operation and resist corrosion so that
adequate service life will be obtained. Positive grids or, more properly, support structures
can be made from pure lead or from lead alloys. While the vast majority of batteries have
some kind of grid structure to hold the paste, in the newer spiral-wound designs the paste
is applied to a lead foil instead of a grid.

Grids can be made in a variety of ways, for example:

• book mold casting

• continuous casting
• expanded metal
• stamping.

In book mold casting, the grid is cast in a mold directly from molten lead alloy. In
continuous casting, the molten alloy is dispensed onto a rotating wheel and engraved with
the grid pattern. In expanded metal and stamping, the grid is formed mechanically from a
cast or rolled alloy strip. Book mold casting is more suited to small production runs as the
molds on the casting machines can be changed easily and quickly. The other methods,
requiring longer set-up times, suit long production runs of the same grid.

2.9 Grid Alloys

Grid alloys used most widely are lead-antimony (Pb-Sb), lead-calcium (Pb-Ca) and lead-
calcium-tin (Pb-Ca-Sn). The alloying metals increase the mechanical strength of the lead,
increase its creep resistance and improve its castability. These alloys are less corrosion-
resistant than pure lead. Thus, other additives are used to modify the grain structure and
reduce corrosion. Lead-antimony alloys are generally used in batteries that require deep
discharges and long cycle lives. Lead-calcium(tin) alloys are used where the duty cycle
requires high-rate discharges and shallow cycling. Some applications of the two classes
of alloys are shown in Table 2-8.
Battery Application Alloy Characteristics
Engine Starting Lead-calcium(tin) Good high-rate performance
Automobiles Low gassing rate
Trucks Low self-discharge rate
Lawn Mowers Poor recovery from deep discharge
Recreation Vehicles
Aircraft
Motive Power Lead-antimony Good cycle life
Materials Handling Higher gassing rate
Airport Tugs Higher self-discharge rate
Golf Cars Good deep-discharge recovery
Mining Vehicles
Standby Power Lead-calcium(tin) Good high-rate performance
Low float currents
Low water loss
Low maintenance
Lead-antimony Good choice for applications where

duty cycle involves cycling

Valve-Regulated Lead-calcium-tin Good high-rate performance
Some cycle capability
Low water loss
Low maintenance

Table 2-8: Applications of lead-antimony and lead-calcium(tin) alloys

Lead-calcium alloys are used in lead-acid battery grids, as calcium has proven to be a
beneficial hardening agent. Figure 2-2 is a phase diagram to aid understanding of the
hardening process. A phase diagram shows the different phases that occur in a mixture of
metals as functions of the relative amounts of the metals and the temperature. Lead-
calcium alloys are strengthened by precipitation of a calcium-rich intermetallic
compound from a supersaturated solid solution. Supersaturation occurs when the molten
alloy is cooled rapidly, for example, during grid casting. Considering the region marked α
in Figure 2-2, the strengthening results from a dispersion of the second phase throughout
the matrix. As revealed in the diagram, above 0.07% Ca, Pb3Ca crystals are formed.
Below 0.07% Ca, Pb3Ca crystallites are found in the alloy, contributing to the strength by
impeding grain boundary mobility.

Figure 2-2: Lead-calcium phase diagram

Lead-antimony alloys are also used in lead-acid batteries, as antimony is another
effective hardening agent for lead. The phase diagram for the lead-antimony binary
system is shown in Figure 2-3. The diagram reveals that for antimony concentrations
lower than 3.5%, the alloys are age-hardenable and can be strengthened by formation of
supersaturated solutions. This occurs when the alloy is cooled rapidly during grid casting.
In this respect, antimony and calcium alloys display similarities both are hardenable by
the formation of supersaturated solutions. In antimony alloys, precipitation of antimony
occurs from the supersaturated solution. Between antimony concentrations of 3.5% and
11.1%, a two-phase structure of the α plus eutectic is formed when cooled to room
temperature. The eutectic acts as a stiffening framework for the solid solution. As the
amount of antimony is increased, increasing amounts of eutectic (α +β) are formed up to
the eutectic composition of 11.1% antimony. At this point, the alloy reaches its maximum
strength. This framework of eutectic in the solid solution can cause the alloy to become
brittle and prone to cracking.

Figure 2-3: Lead-antimony phase diagram

When tin is added to lead-antimony alloys, it increases the strength by forming an

antimony-tin precipitate in the solid solution.

Age hardening refers to the fact that hardening by precipitation of phases from a
supersaturated solution is a time-dependent process hardness increases progressively with
time after casting. The newly cast grids are soft and flexible, requiring aging for a certain
amount of time before they are strong enough to be pasted.

It is common to age harden lead-calcium grids for up to three days and lead-antimony
grids for up to two days before pasting. Figure 2-4 shows the ultimate tensile strength of
a 0.08% calcium alloy after various aging times.

Figure 2-4: Aging characteristics of lead-0.08% calcium alloys

The air-cooled alloys reach about 80% of their fully aged strength within 24 hours of
casting and then slowly increase in strength over time, reaching a level of about 5,000
psi. If the grids are quenched in water, they are considerably harder, reaching a fully aged
hardness of about 6,300 psi. This is probably due to a greater degree of supersaturation in
the solid solution that results in increased precipitation and strengthening.
The effect of adding tin to the alloy is shown in Figure 2-5.

Figure 2-5: Aging characteristics of cast, air cooled, lead-calcium-tin alloys

Alloy compositions used by battery manufacturers are different for each application.

Automotive battery-grid alloys, since the 1970s, have been the lead-calcium(tin) type
almost without exception: a result of the introduction of maintenance-free designs where
it is either difficult or impossible to add water. Thus, alloys that minimized water loss
during charging were required. For some years, alloys containing a lower amount of
antimony were used, but since the 1970s they have been gradually phased out in favor of
lead-calcium(tin) systems. Table 2-9 lists examples of widely used low-antimony and
lead-calcium alloys. The first calcium alloys did not incorporate aluminum. It was added
in the late 1970s to prevent calcium loss in the melt pot. Positive plate-grid alloys have
also been developed with higher tin levels to provide improved conductivity of the
grid/active material interface. An example is shown in Table 2-10.

Lead-Antimony Lead-Calcium
Element Concentration (%) Element Concentration (%)
Antimony 2.50-3.00 Calcium 0.120-0.150
Tin 0.20-0.35 Aluminum 0.020-0.030
Arsenic 0.15-0.25 Tin 0.010 max.
Copper 0.050-0.080 Antimony 0.0010 max.
Silver 0.01 max. Arsenic 0.0015 max.
Bismuth 0.05 max. Silver 0.0050 max.
Iron 0.001 max. Bismuth 0.025 max.
Nickel 0.0015 max. Copper 0.0025 max.
Iron 0.0010 max.
Nickel 0.0003 max.
Tellurium 0.003 max.
Zinc 0.0010 max.

Table 2-9: Typical maintenance-free alloys used in automotive battery positive grids

Element Concentration (%)

 Calcium 0.085-0.100
Aluminum 0.020-0.030
Tin 0.50-0.60
Antimony 0.0005 max.
Arsenic 0.0005 max.
Silver 0.005 max.
Bismuth 0.025 max.
Copper 0.001 max.
Iron 0.001 max.
Nickel 0.0003 max.
Tellurium 0.0001 max.
Zinc 0.0005 max.

Table 2-10: Positive grid alloy with enhanced conductivity of the grid/active material
interface

The use of low-antimony alloys in maintenance-free automotive batteries was greater in

Europe than in the United States. To reduce gassing to the lowest level possible
consistent with good castability, an alloy was developed with antimony in the
concentration range of 1.3%-1.5%. It was used in both positive and negative grids. A
typical specification for the alloy is shown in Table 2-11. Selenium is added to the alloy
as a grain refiner to improve castability.

Element Concentration (%)

Antimony 1.30-1.54
Tin 0.15-0.25
Arsenic 0.10-0.20
Selenium 0.013-0.023
Copper 0.02 max.
Sulfur 0.0015 max.
Silver 0.01 max.
Bismuth 0.05 max.
Iron 0.002 max.
Nickel 0.0015 max.

Table 2-11: Typical specification for very-low-antimony alloy used in automotive battery
positive and negative grids
Calcium alloys were used in automotive battery negative grids before being used in
positive grids, because grid corrosion is insignificant at the negative plate; thus, there is
no problem with a passivating-corrosion-layer build-up between the grid and the active
material. A common specification for a negative-grid alloy with rapid-hardening
characteristics and with aluminum to prevent calcium loss is shown in Table 2-12.

Element Concentration (%)

Calcium 0.120-0.150
Aluminum 0.020-0.030
Tin 0.010 max.
Antimony 0.0010 max.
Arsenic 0.0015 max.
Silver 0.0050 max.
Bismuth 0.025 max.
Copper 0.0025 max.
Iron 0.001
Nickel 0.0003
Tellurium 0.0003
Zinc 0.001

Table 2-12: Negative-grid alloy for rapid hardening for automotive batteries

Recently, automotive battery manufacturers have started to use elevated silver levels in
positive-grid alloys to reduce corrosion and increase creep resistance at high
temperatures. This practice is becoming widespread as under-hood temperatures continue
to increase. An example of a calcium/tin/silver alloy is shown in Table 2-13.

Element Concentration (%)

Calcium 0.0300-0.0550
Aluminum 0.008-0.018
Tin 0.550-0.800
Antimony 0.002 max.
Arsenic 0.002 max.
Silver 0.0300-0.0350
Bismuth 0.025 max.
Copper 0.0025 max.
Iron 0.001
Nickel 0.0003
Tellurium 0.0003
Zinc 0.001

Table 2-13: Calcium/tin/silver alloy for high-temperature corrosion and creep resistance

Automotive battery plates are welded together in the cells using the cast-on-strap
process. A good cast-on-strap alloy has a moderate amount of eutectic (27%-45%) to
facilitate easy bonding to the lugs and terminals. The alloy has a large slushy region
making it ideal for joining materials. It also contains moderate amounts of copper and
selenium as nucleants. A cast-on-strap alloy is also often used for small parts casting.
Three cast-on-strap alloys are shown in Table 2-14. The first is general purpose, the
second has greater ductility to resist vibration and the third uses selenium in lieu of
copper and sulfur as nucleants.

General Purpose Alloy High-Ductility Alloy Selenium Alloy

Element Concentration (%) Element Concentration (%) Element Concentration (%)
Antimony 2.90-3.25 Antimony 2.95-3.25 Antimony 3.00-3.30
Tin 0.15-0.25 Tin 0.10-0.15 Tin 0.04-0.07
Arsenic 0.15-0.30 Arsenic 0.10-0.20 Arsenic 0.04-0.07
Copper 0.050-0.065 Copper 0.02 max. Selenium 0.012-0.018
Sulfur 0.0005-0.0020 Sulfur 0.0015 max. Copper 0.05 max.
Silver 0.06 max. Silver 0.01 max. Sulfur 0.001 max.
Bismuth 0.05 max. Bismuth 0.05 max. Silver 0.004 max.
Calcium 0.0015 max. Iron 0.002 max. Bismuth 0.03 max.
Iron 0.0015 max. Nickel 0.0015 max. Iron 0.001 max.
Nickel 0.001 max. Nickel 0.001 max.

Table 2-14: Examples of cast-on-strap alloys

Motive-power batteries use antimonial-alloy positive grids to achieve long cycle lives.
The antimony concentration varies from 5%-6%. Table 2-15 shows examples. Note the
use of selenium as a grain refiner in the 5% alloy.

6% Antimony 5% Antimony
Element Concentration (%) Element Concentration (%)
Antimony 5.75-6.25 Antimony 4.90-5.30
 Tin 0.45-0.55 Tin 0.15-0.40
Arsenic 0.10-0.15 Arsenic 0.10-0.20
Copper 0.05-0.07 Selenium 0.02-0.03
Sulfur 0.006-0.008 Copper 0.03 max.
Silver 0.01 max. Sulfur 0.002 max.
Bismuth 0.045 max. Silver 0.01 max.
Iron 0.002 max. Bismuth 0.05 max.
Nickel 0.001 max. Iron 0.002 max.
Nickel 0.0015 max.

Table 2-15: Motive-power antimonial positive grids

In tubular plate design of motive-power batteries, positive-plate spines are cast from an
alloy with a higher amount of antimony to improve flow characteristics into the tube
mold. The eutectic composition of 10.5% antimony is often used. Table 2-16 shows the
composition of a typical spine alloy.

Element Concentration (%)

Antimony 10.25-10.75
Tin 0.03-0.05
Arsenic 0.25-0.35
Copper 0.02-0.05
Sulfur 0.002-0.006
Silver 0.015 max.
Bismuth 0.05 max.
Iron 0.005 max.
Nickel 0.002 max.

Table 2-16: 10.5% antimony alloy for tubular plate spines

Standby-power and valve-regulated batteries use lead-calcium alloys for both positive
and negative grids. Batteries designed for cycling service have alloys with a significant
amount of tin, while batteries designed for float service contain less tin. Examples are
shown in Table 2-17.

Batteries for Cycling Service Batteries for Float Service

 Element Concentration (%) Element Concentration (%)
Calcium 0.085-0.100 Calcium 0.060-0.066
Aluminum 0.020-0.030 Aluminum 0.011-0.019
Tin 1.40-1.60 Tin 0.55-0.61
Antimony 0.001 max. Antimony 0.001 max.
Arsenic 0.0005 max. Arsenic 0.0015 max.
Silver 0.005 max. Silver 0.005 max.
Bismuth 0.025 max. Bismuth 0.025 max.
Copper 0.001 max. Copper 0.0025 max.
Iron 0.001 max. Iron 0.001 max.
Nickel 0.0003 max. Nickel 0.0003 max.
Tellerium 0.0001 max. Tellerium 0.0003 max.
Zinc 0.0005 max. Zinc 0.001 max.

Table 2-17: Lead calcium grids for standby-power and valve-regulated batteries