Prof. Detchko Pavlov, D.Sc.

Institute of Electrochemistry and Energy Systems (former CLEPS)

Bulgarian Academy of Sciences, Sofia 1113, Bulgaria

Lecture course: Lead-Acid Batteries

Chapter technology
1
Essence of the technology of plate manufacture

Paste Cured paste Formed PAM

4BS

Solution Pores PAM agglomerate

Crystals Crystals

3BS

Paste preparation – formation of the building elements (3BS, 4BS crystals) of

the porous structure of the active masses
Pasting of the grids – connection of the paste to the current collector (grid)
Curing of the plates – 3BS, 4BS, PbO particles interconnect to build a hard
porous skeleton system
Formation – the cured paste is converted into positive and negative active mass
2
 Aim of the technological process
of paste preparation

To produce the building elements ("bricks") of which the skeletons of

the two types of active masses are built

Basic topics to be discussed in the lecture

1. Thermodynamics of the PbO/H2SO4/NaOH system

2. Overview of the raw materials for paste preparation

3. Physico-chemical processes during preparation of 3BS pastes

4. Physico-chemical processes during preparation of 4BS pastes

and parameters affecting these processes

5. Technological parameters of the paste and their relation to

its phase composition

3
Solubility of lead compounds vs. pH of the solution

PbO/H2SO4 / NaOH system aSO42- = 1

25oC: PbSO4 pH < 8.4

PbO.PbSO4 pH = 8.4-9.6
3BS pH = 9.6-14.4
5PbO2.H2O pH > 14.4

80oC: orthorhombic PbO

4BS

in alkaline solutions - HPbO2-

in acidic solutions - Pb2+
4
Basic raw materials for paste preparation

5
 Additives to negative pastes

1. Expanders (organic surfactants) - 0.15 - 0.5%

salts of the ligno-sulphonic acid
• Vanisperse, Skitan EZE • Indulin • humic acid

2. BaSO4 (0.4 - 1.2%) - nucleant for PbSO4 crystals

isomorphism between PbSO4 and BaSO4
ensuring uniform distribution of PbSO4
throughout the internal surface of NAM

3. Carbon black - 0.1 - 0.3%

improves the electric conductivity of NAM
at the end of discharge

6
 Additives to negative pastes

4. Inhibitors - absorbed at the Pb surface - 0.1-0.2%

suppress the reactions
Pb + H2SO4  PbSO4 + H2
Pb + 1/2 O2  PbO
PbO + H2SO4  PbSO4 + H2O
without affecting the rate of the discharge reaction
Pb + H2SO4  PbSO4 + 2H+ + 2e-
(efficient  PbSb grids)
- zinc stearate, - and - naphtol, -nitroso--
naphtol, m-aminophenol

5. Polymeric additives - usually suspensions as:

polyvinyl pirrolydone, polyvinyl alcohol, polyacrilic
acid, polyethylen oxide, polystyrenesulfonic acid
7
 Additives to positive pastes

1. Retainers (stabilizing additives) - 0.2 - 0.4%

 retain the skeleton of PAM from disintegration during cycling
 reduce technological waste during technological operation
polyester fibres
Chopped polyethylene fibres length 2-4 mm
polypropylene fibres, etc
2. Conductive additives
 improve the efficiency of formation
 improve the current acceptance of deeply discharged batteries
Carbon
inert conductive fillers
carbon emulsion
3. Binders (Active ions ) (Sb5+, Sn4+, Bi3+, As3+ etc.)
• improve the electric conductivity of gel zones in the PbO2 AM
• added as alloying additives (Sb, Sn, etc.) to the grid alloys,
on corrosion of the grid they are absorbed by the active mass
and improve the connection between corrosion layer and PAM
8
 Influence of temperature
on phase composition of the paste

80
Relative Intensity (%)

60

40

20

0
20 30 40 50 60 70 80 90 100
Temperature of paste

6% H2SO4/ Leady oxide

40 min stirring
20-45oC - 3BS + ort-PbO + tet-PbO
45-70oC - 3BS + 4BS + tet-PbO + ort-PbO
70-90oC - 4BS + tet-PbO + ort-PbO 9
Tribasic lead sulfate pastes

3PbO.PbSO4.H2O

3BS

10
 Kinetics of the processes during
3BS paste preparation
100

4.5 % H2SO4 , D = 3.70 g.cm-3

80

60
4PbO + H2SO4  3PbO.PbSO4.H2O + Q
In/SIn, %

40

20
5kg paste batch:
0 Barton leady oxide, H2SO4 solution
0 10 20 30 40
Time, min 1.40 g/cm3

30 H2SO4/PbO ratio 4.5%,

initial temperature 22oC
Temperature, oC

28

26 duration of mixing 30 min

24

22

20
0 10 20 30
Time, min 11
3PbO.PbSO4.H2O pastes

3BS particles length 1-3 µm

diameter 0.2-0.6 µm
12
 Dependence of phase composition of the paste
on the H2SO4/PbO ratio
Conditions: temperature 35oC, ball mill leady oxide,
H2SO4 solution 1.40 g/cm3
5 kg paste batch, time of mixing 40 min
Characteristic diffraction lines for:

tet-PbO d = 0.280 nm
orthorhombic-PbO d = 0.295 nm
PbO.PbSO4 d = 0.333 nm
3BS d = 0.325 nm
Pb d = 0.284 nm

Reactions: chemical equations

1) tet-PbO  orthorhombic-PbO
2) 4PbO + H2SO4  3PbO.PbSO4.H2O (7.75% H2SO4/PbO)
3) 2PbO + H2SO4  PbO.PbSO4 + H2O
a) max 3BS  10% H2SO4 (theoret. H2SO4/PbO = 7.75%)
b) tet-PbO  12% H2SO4/PbO
Conclusions: a) paste contains amorphous PbSO4-containing compounds
b) the paste is a non-equilibrium system
13
 Changes in phase composition of pastes prepared at 30oC
vs. H2SO4 content

a
80 a) without expander and BaSO4
60

40

20
Relative intensity (%)

b
80 b) with 0.5% BaSO4
60
BaSO4 has no substantial effect
40
on the processes in the paste.
20

c c) with 0.5% BaSO4 and 1% expander A-72

80

60 The expander suppresses the

40
formation of orthorhomb-PbO.

20

2 4 6 8 10 12
H2SO4 (%) 14
Tetrabasic lead sulfate pastes

4PbO.PbSO4

4BS

15
 Kinetics of 4BS crystal formation
100 100
Changes in phase composition
80 80 and temperature during
preparation of two pastes with
In / SIn,%

60 60 H2SO4/PbO = 6% identical initial composition

d = 3.85 g.cm-3
H2SO4/PbO = 6% and conditions of preparation.
40 40
d = 3.80 g.cm-3 Paste 2 contains 3% of paste
20 20 No.1 at the beginning of
preparation
0 0
0 10 20 30 cp 0 10 20 30 cp

95 95
Temperature, oC

4BS nucleation is the

slowest elementary process
90 90

85 85

80 80
0 10 20 30 40 0 10 20 30 40
Time, min Time, min

4PbO + H2SO4  3PbO.PbSO4.H2O

2(3PbO.PbSO4.H2O) + tet-PbO + ort-PbO  2(4PbO.PbSO4) + 2H2O
16
 4PbO.PbSO4 pastes

4BS particles length 15- 40 µm

diameter 3- 6 µm
17
 Phase composition vs. time of paste mixing

100 100 100

80 80 80
70 oC 80 oC 90 oC
60 60 60

In / SIn,%
In / SIn,%

40 In / SIn,%
40 40

20 20 20

0 0 0
0 10 20 30 0 10 20 30 0 10 20 30
Time, min Time, min Time, min

With temperature increase, nucleation and growth

of 4BS crystals is accelerated

Some authors report of formation of 4BS at room temperature

after 1-month stay of the paste in hermetically closed containers.
18
Phase composition of a paste prepared at 80oC vs. the amount of H2SO4
expressed as a % content with respect to the quantity of leady oxide

60
Relative intensity Ia / SIn (%)

40

20

0 Stoichiometric equations:
0 2 4 6 8 10 12
Amount of H2SO4 (%)

Stoichiometric equotions:

4PbO + H2SO4  3PbO.PbSO4.H2O

2(3PbO.PbSO4.H2O) + tet-PbO + ort-PbO  2(4PbO.PbSO4) + 2H2O
6.15% H2SO4/PbO - the whole amount of PbO should be converted into 4BS
19
Changes in phase composition of a paste prepared at 80oC
vs. percent content of H2SO4

a
80

60 (a) Without expander

40 (b) 0.5 BaSO4
20 (c) 0.5 BaSO4 and 1% expander A-72
Relative intensity Ia / SIn (%)

80 b

60

40

20

80 c
1. Expanders block the formation
60
of orthorombic PbO and 4BS
40 2. BaSO4 does not affect
20 substantially the processes of
4BS formation
0
0 2 4 6 8 10 12
H2SO4 (%) 20
 Changes in phase composition of the paste
during formation of 4BS

(Expander is added at the 20th min)

60
Relative intensity (%)

40

20

0
0 20 30 40
Time, min

1. The introduction of expander into the paste causes transformation of

orthorhombic-PbO into tetragonal-PbO and stops the formation of 4BS

2. Hypothesis: blocking of the formation of 4BS is due to the lack of

orthorhombic-PbO in the paste
21
 Technological parameters of the pastes
and their dependence on phase composition

22
 Technological scheme

Paste preparation
Grigs
phase. chem.
Leady oxyde comp comp. weight density

Water Mixing Pasting Wet

machine Paste machine pasted
plates tempe humi
Sulphuric acid rature dity

Additives tempe visco consis Pasted

time rature sity density tency Tunel
plates
drier
Initial Mixing
materials conditions

Paste
tempe speed Curing
characteristics rature

23
Paste density vs. amount of H2SO4 at constant quantity
of liquid components and leady oxide

4.4

4.4
Density (g.cm-3)

4.2

4.0

3.8
0 100 200 300 400 500

Amount of H2SO4 (ml) – 2kg leady oxide

Paste density does not depend on the ratio between the amounts of the
different phases present in the paste, but on the ratio between the liquid
and solid components.
24
 Paste consistency

Paste consistency vs. amount of H2SO4 16

Consistency of relative units

at constant quantity of the liquid 14
components and 2 kg leady oxide
12

16 10
Consistency of relative units

8
12

8 0 2 4 6 8 10 12
Amount of H2SO4 , %

4
Consistency of the paste vs. amount of
H2SO4 at constant quantity of the liquid
0 100 200 300 400 500
H2SO4, ml components and 2 kg leady oxide

25
Effect of expanders on paste consistency

15

Hydrolytic

Consistency in relative units

lignin

Without
10
expander

Lignin - M

5
1.0 1.5 2.0
Amount of H2O, l

Lignin M reduces the consistency of the paste compared with

that of the expander-free formulation.
The hydrolytic lignin increases the consistency.
Expanders exert no effect upon the density of the paste
26
 Capacity vs. number of cycles as a function
of phase composition of the paste

120 30 oC

100
Capacity (C20), %

0%
4%
80 6%
8% 0% H2SO4  tet-PbO very low capacity
12 %
60 8%
H2SO4 3BS, 1BS high capacity, short cycle life
40 12%

120 4%
80 oC
H2SO4 4BS long cycle life
100
6% 80oC
Capacity (C20), %

4%
80 H2SO4  3BS shorter cycle life than that of
6% 30oC plates prepared with 4BS
60

40

0 50 100 150 200

Cycles
27
 Paste preparation
with H2SO4 1.18kg/l and H2O

LO

Mix (2’) Additives + Fibers

H 2O
H2SO4 1.18kg/l
Mix (3’)
The H2SO4 solution is
8-10’ poured into the mixer at
a rate that keeps t < 60oC

Mix (15-20’)

Pasting the grids

28
 Paste preparation
with H2SO4 1.40kg/l and H2O

LO

Mix (2’) Additives + Fibers

Mix (3’) H 2O
1-2’

Mix (5-8’) H2SO4 1.4kg/l

5-10’
The H2SO4 solution is
poured into the mixer at Mix (15-20’)
a rate that keeps t < 60oC

Pasting the grids

29
Negative paste preparation
with H2SO4 1.40kg/l and H2O

LO Expanders
Carbon
Mix (2-3’) Fibers
BaSO4
Mix (5-8’) H 2O
1-2’

Mix (5-7’) H2SO4

5-10’

Mix (15’)

Pasting the grids 30

 Summary
1. Raw materials for paste preparation
a) leady oxide + H2O + H2SO4 solution
b) additives I negative paste: expanders, inhibitors
I positive plates: retainers, conductive additives
2. 3BS paste
a) to < 60oC
b) H2SO4 < 6%
c) tet-PbO, ort-PbO < 5%
d) Expanders inhibit the formation of ort-PbO from tet-PbO
3. 4BS paste
a) to > 70oC
b) H2SO4 < 6%
c) obtained from 3BS + tet-PbO + ort-PbO
d) the rate of nucleation is a limiting process for 4BS formation
e) orthorhombic PbO < 20%
f) expanders block the formation of 4BS
4. Paste density depends on: liquid/leady oxide ratio
Paste consistency = f (phase composition, density)
5. The phase composition of the paste influences the parameters of the positive plate:
a) PbO – low capacity – long cycle life
b) 1BS – high capacity – short cycle life
c) 3BS – high capacity – long cycle life
d) 4BS – moderate capacity – long cycle life 31
Thank you for your attention!

32
 Mass
Molality Molarity Density
Fraction
m2 H2SO4 M2 H2SO4  Mass fraction 100 w2,
(100 w2)
H2SO4
(mole/kg) (mole/liter) (kg/liter)
Molality m2,
3.929 0.417 0.4097 1.0229
7.000 0.767 0.7447 1.0434
Molarity M2,
10.000 1.133 1.085 1.0640 Density 
14.56 1.738 1.628 1.0962
for the water/sulfuric
19.80 2.517 2.291 1.1351
25.31 3.455 3.038 1.1774 acid system
29.47 4.260 3.637 1.2107
34.28 5.318 4.370 1.2503 Haase et al. (1966)
39.10 6.546 5.148 1.2913
43.94 7.992 5.977 1.3340
48.71 9.683 6.846 1.3787
53.48 11.721 7.775 1.4258
58.35 14.284 8.782 1.4762
63.10 17.435 9.830 1.5278
67.54 21.215 10.86 1.5776
72.28 26.586 12.03 1.6325
77.05 34.250 13.27 1.6885
81.87 46.042 14.54 1.7423
85.93 62.270 15.60 1.7810 33