Raw Materials for Manufacture of Lead-

Acid Batteries

Dr. P.G. Balakrishnan

 Raw Materials for manufacture of lead-acid batteries
Metals Plastics Chemicals

Lead (Pb) 1. Poly propylene (PP) 1.Sulphuric acid (H2SO4)

Antimony (Sb) 2. Copolymers of PP (PPCP) 2. Lead oxides
Tin (Sn) 3. Acrylo buta dienes- 3.Carbon black (CB)
syrene co-polymer (ABS)
Arsenic (As) 4. polyvinyl chloride (PVC) 4. Blanc fixe (BaSO4)
Selenium (Se) 5. poly ethylene (PE) 5. Lignins
Calcium (Ca) 6. Polystyrene (PS or HIPS) 6. Carboxy methyl cellulose (CMC)
Copper (Cu) 7. Sodium sulphate (Na2SO4)
Alumunium 8. Sodium lauryl sulphate (SLS)
(Al)
9. Stearic acid
10. (NH4)2SO4 Ammonium sulphate
11. (S)
12. o-Phosphoric acid (H3PO4)
13. Blown Bitumen
14. Other sealants like epoxy resins
 Characteristics of lead
Properties Data
Atomic weight (AU) 207.19
Atomic Number 82
Electronic configuration [Xe]54 4f 14 5d10 6s2 6p2 [

Number of electrons participating in the 2 (6p2)

cell reaction
Lead compounds (Oxidation state) +2 and +4 valence (amphoteric)
Density (kg L-1) 11.341 at 25C (increases on rolling)
Melting point (C) 327.43
Boiling point (C) 1750 at one atmosphere pressure
Liquid density at melting point (kg L-1) 10.66

Specific resistance (. cm x 10-6 ) 6.02 ( - 183C); 14.1 (- 78C)‘ 20.4 (0C)
Temperature coefficient of electrical 20.65 (25C) (207 n. M); 28.0 (91C)
resistivity = 4.2 x 10-3 C-1 94.0 (318C); 107.2 (600C)
Electrical conductivity (MS/m) 5.95 (0C); 4.826 (18C)’ 1.06 ((327C))
Thermal conductivity [W (m. K)-1] 35.3
Thermal Expansion [µm (m.K)-1] 28.9 at 25ºC
Viscosity (Ns m-2) 2.315 x 10-3 at 400C
Heat of fusion (kJ mol-1) 4.77
Heat of vaporization (kJ mol-1) 179.5
Heat capacity (J (kg.K)-1 127.7
structure FCC
Electro-negativity (Pauling Scale) 2.33
Ionization energy (kJ mol-1) First 715.6; Second 1450.5; Third 3081,5
Radii (pm)
Atomic 180
Covalent 147
Van der Waals 202
Magnetic ordering Diamagnetic
Trends in the use of lead metal
 Year-wise break-up for mine production of lead metal
(Thousand metric tons)
Country 2005 2006 2007 2008
USA 440 429 444 440
Australia 760 686 641 576
Canada 77 82 82 95
China 950 1200 1500 1540
India 50 67 78 85
Ireland 70 62 54 56
Kazakhstan 40 48 40 47
Mexico 143 120 120 145
Morocco 65 45 45 35
Peru 310 313 329 335
Poland -- 51 85 53
South africa 40 48 42 48
Sweden 35 77 62 69
Other countries 300 240 480 300
World total 3280 3468 4002 3824
Trend in the use pattern of lead metal
 Manufacture of Gray oxide of lead (Leady oxide)
Lead oxides are produced by thermal processes in which
lead is directly oxidized with air. The processes may be
classified according to the temperature of the reaction:
low temperature (< 327ºC)
moderate temperature (327 to 888ºC) and
high temperature. ( >888ºC)
 Ball mill oxidee
 Low Temperature Oxidation, below the melting point of
lead (< 327ºC): Low temperature oxidation of lead is
accomplished by tumbling slugs of metallic lead in a ball mill
equipped with airflow. The airflow provides oxygen and is
used as a coolant. If some form of cooling were not supplied,
the heat generated by the oxidation of the lead plus the
mechanical heat of the tumbling charge would raise the charge
temperature above the melting point of lead. The ball mill
product is a "leady" oxide with 20 to 50 percent free lead.
 The exothermic process produces a heat energy of 983 kJ kg-1
 This type of oxide contains mostly tetragonal modification.
 Barton Pot process
 The Barton Pot process uses a cast iron pot with an upper and
lower stirrer rotating at different speeds. Molten lead is fed
through a port in the cover into the pot, where it is broken up into
droplets by high-speed blades. Heat is supplied initially to develop
an operating temperature from 370 to 480°C. The exothermic heat
from the resulting oxidation of the droplets is usually sufficient to
maintain the desired temperature. The oxidized product is swept
out of the pot by an air stream. The operation is controlled by
adjusting the rate of molten lead feed, the speed of the stirrers, the
temperature of the system, and the rate of air flow through the pot.
The Barton Pot produces either litharge or leady litharge (litharge
with 50 percent free lead). Since it operates at a higher temperature
than a ball mill unit, the oxide portion will usually contain some
orthorhombic litharge. It may also be operated to obtain almost
entirely orthorhombic product.
1. Lead Melting Pot 7. Rotary Seal Valve
2. Control Panel 8. Connecting screw conveyor
3. Reaction Pot 9. Dust Collector
4. Connecting Duct 10. Rotary Valve
5. Classifier 11. Exhaust Fan
6. Cyclone
Linklater Pot Process
High Temperature above the melting point
of orthorhombic lead monoxide (>888ºC)
High temperature oxidation is a fume-type process. A
very fine particle, high-purity orthorhombic litharge is
made by burning a fine stream of molten lead in a
special blast-type burner
The flame temperature is around 1200°C. The fume is
swept out of the chamber by an air stream, cooled in a
series of "goosenecks" and collected in a bag house.
The median particle diameter is from 0.50 to 1.0
micrometers, as compared with 3.0 to 16.0
micrometers for lead monoxide manufactured by other
methods.
 Relative merits of Barton-Pot and
Ball Mill Lead oxides
Parameter Barton-Pot Ball mill
Economics Lower initial cost (67%) Initial cost more (100%)

Operation Higher output per unit More space required

space, More noise
Comparatively quiet Higher maintenance cost
Harder to control More power required
Maintenance cost lower
Lesser power required

Energy 100 100 to >300

requirement
(kWh t‑1)
 Relative merits of Barton-Pot and Ball Mill Lead oxides
(Contd.)

Oxide Properties Barton-Pot Ball mill

Spontaneous combustion
More stable; easier to More consistent in quality; More
handle; longer shelf life reactive
May cause problems in storage
and transport, because of fine
particles

Acid adsorption* (mg/g ) Less (200 – 300) more (260 – 280)

Particle size (μm) Coarser (8) finer (5)
Surface area (BET, m2g-1) low (1.2 – 1.4) high (2.4 – 2.8)
Apparent density (Scott No., g cm-3) 1.1 – 1.7* 1.4 – 2.3

Polymorphism 60-70 wt.% -PbO 15 wt.% -PbO

1-4 wt.% -PbO

Tamped density (g cm-3) 3.2 to 3.8 2.9 to 3.5

JEL Volumeter
Reactivity Good Excellent
Deviation of PbO % 2 1
 Relative merits of Barton-Pot and
Ball Mill Lead oxides (Contd.)

Flat Softer paste, easier Stiff paste requiring

plates/Tubula pasting. strict control.
r plates Curing rate average. Faster Curing.
Easier filling of tubular Stronger material
plates
performance More life, but lower Shorter life, higher
initial Ah initial capacity
Production 300-800 Up to 1000
rate (kg h-1)
Reactivity good excellent
 Red lead (Pb3O4) is a mixture of
2PbO + PbO2
 Red lead is prepared in mechanical furnaces by the oxidation of PbO batches (usually
orthorhombic Barton oxide) within the temperature range 470°C- 520°C. The oxidization
rate depends on:
 The oxygen pressure
 The surface of the oxide powder subjected to oxidation and
 The temperature of the furnace.
 PbO is ground prior to oxidation. The percentage of Pb 3O4 in the charge increases with the
time, and the oxidation rate remains constant up to 70%-80% red lead, and then slowly
decreases. The red lead is ground before use in battery manufacture. The same furnaces
can be used for the polymorphic transition of orthorhombic-PbO into tetragonal-PbO.
Stirring the charge of orthorhombic-PbO for 2-3 h at a convenient temperature below
400°C results in this conversion.
 Since red lead already contains PbO 2 up to 30%, the formation of the positive plates with
red lead will be shortened and that of negative plate prolonged because the energy required
for conversion to PbO2 is decreased, and that required for conversion to Pb is increased
Current-voltage relationship during the charging of negative plates made
with primary high-purity lead and lead with higher impurity
 Evaluation of oxides
Chemical composition
Free lead content
Scott Number (Apparent density)
Tamped density (JEL Volumeter)
Acid absorption number
Water absorption number
BET surface area
Particle size distribution
Morphology of the particles
 Characteristics of oxides
The kinetics of reactions at electrode/electrolyte
interfaces of electrochemical power sources are
affected by several physical properties of the
electrodes and other factors, which control bulk
chemical reactions Some of the physical
properties are:
Interfacial surface area between the electrode
and electrolyte
That between the active material and the
current carrier
The number, size, shape and distribution of the
pores in the electrodes and
The electrical conductivity of the active
material, reaction products and electrolyte.
 Properties of other metals
Metals At. At. Density M. Pt B. Pt
No. weight (kg L-1) (ºC) (ºC)
Aluminium (Al) 13 26.98 2.7 660 2467
Calcium (Ca) 20 40.08 1.55 839 1484
Copper (Cu) 29 63.55 8.96 1083 2567
Arsenic (As) 33 74.92 5.72 81 613
Selenium (Se) 34 78.96 4.79 217 685
Silver (Ag) (Argentum) 47 107.87 10.5 962 2212
Tin (Sn) (Stannum) 50 112.4 8.65 321 765
Antimony (Sb) 51 121.76 6.68 630.9 1750
(Stibnum))
 Paste Additives
S.No. Name Per cent Effect Functions
added

1. Lampblack 0.2 – 2.0% Decrease end-of- Improves

charge voltage conductivity and
cold starting

2. Blanc fixe 0.3 – 2.0% No change in voltage Provides

nucleation sites
for PbSO4
3. Organic 0.2% - Raises the end-of- Prevents the
0.7% charge voltage by formation dense
0.2V/cell at 0.1C20 insulating lead
amperes charging sulphate layers
 Water
The water should be of the distilled or
demineralised one with
solid matter within the range of 100 - 1000 ppm,
constituted mainly by the magnesium and calcium
salts.
Colourless and odourless and
Should not contain any oil drops visible to the
naked eyes.
 The conductivity must be less than 10-5 / ohm-cm.

The pH value must be in the range 5 and 7.

The organic impurities as determined by
permanganate consumption should be less than 20
mg per litre.
 Carbon Black in NAM
Carbon functions primarily as a conductor, and thereby
enhances formation efficiency and reduces the level of
residual sulphate. It may also improve recharge,
particularly under deep-discharge conditions.
Increasing amounts of carbon in NAM of VRLAB reduced
the PbSO4 accumulation and extended the life performance
in the simulated cycle-life test
Carbon formed a conductive network on PbSO4 particles of
the discharged negative plates. the specific surface area
(SSA) may be more important,
C increases conductivity This alone is not responsible for
the effect, however, because different types of carbon,
which gave similar improvements in conductivity,
conferred quite varied benefits on negative-plate
performance
 Carbon Black
This should be a lump-free powder. It should be free
from oily or tarry matter as revealed by a colourless
extract with benzene. The lampblack must have a
minimum 75% wettability initially. (Test: Pour 15 ml
of 1.400 acid at 27oC over 0.5 g of sample in a test
tube. Do not shake).
CB in PAM
called residual factor or reliability factor: It is a measure of the agreement between the crystallographic model and the experimental X-ray diffraction

Isomorphous nature of sulphates of lead,

barium and strontium
PbSO4 BaSO4 SrSO4

R Values* 0. 067 0.043 0.053

Cation-O bond 2.87 2.952 2.831
length (Å)
Sulphur-O bond 1.49 1.478 1.474
length (Å)

*Also called residual factor or reliability factor: It is a

measure of the agreement between the crystallographic
model and the experimental X-ray diffraction data
 Barium sulphate
This should be of the precipitated variety (called
“blanc fixe”) that is almost totally free from iron and
chloride compounds and should pass through 100
mesh screens. Though the percentage added is about
0.1 to 0.3%, one can increase it to 10 times in pastes
that do not contain any organic additive such as lignin.
The ideal sample should contain 98% barium sulphate
with carbonate as BaCO3 0.2% maximum, moisture
0.25 - 1 %, Fe 0.005% maximum, Mg 0.25% and Cl
0.05%. 100% material should be passing through 350
mesh.
 Barium sulphate (Cotd.)
Blanc fixe is a very effective anti-passivating agent; its
small particle size provides millions of sites for
nucleation to take place.
The effect of increasing the content of barium sulphate
on the cold cranking performance is negligible, but it
has a tremendous effect on the life of the battery
 Lignin
Lignin is an organic additive to the negative plate. It
helps in increasing the low temperature high rate
discharge performance. It is a high molecular weight
material obtained from wood materials. The basic
building block is a phenyl propane derivative
The BET surface area of NAM is 0.2 m2 g-1 when there
is no lignin. However when lignin is included in the
paste recipe, these values increase proportionate to the
amount added, reaching a value of 0.5 to 0.8 m2 g-1.
Structure of lignin
Adsorption of lignin on NAM
Diagrammatic representation of effect of lignin on the growth of Pb crystals during
NP formation
during negative-plate formation
Effect of Expanders (Contd.)
Effect of lignin on CV of lead in
H2SO4
Cyclic voltammetry on Pb in H2SO4
 Dynel Fibre
Some manufacturers prefer to add a plastic
fibre known as dynel to strengthen the positive
plates and to reduce the tendency of shedding.
This should be type 150, uncrimped 3 mm and
3denier and must be free of clumps. This
material does not affect the electrical
performance. The usual per centage employed
is 0.025 to 0.1 % of oxide weight. The fibre is
agitated and dispersed in initial water and
added with the initial water addition.