TECHNICAL PAPERS

SOLID-STATE SCIENCE AND TECHNOLOGY

Some Structural and Textural Aspects of Tribasic Lead

Sulfate Precipitation during the Mixing of
Lead-Acid Battery Positive Paste
F. Vallat-Joliveau, A. Delahaye-Vidal, and M. Figlarz
Laboratoire de Rdactivitd et de Chimie des Solides, Universitd de Picardie Jules Verne, URA CNRS 1211,
80039 Amiens Cedex, France

A. de Guibert
C.E.AC, 92111 Clichy Cedex, France

ABSTRACT
The reaction between PbO and H2SO4 in water leading to the formation of tribasic lead sulfate hydrate was studied
using pH measurements, x-ray diffraction, scanning and transmission electron microscopy, and infrared spectroscopy. We
examined the effect of different parameters such as temperature, starting composition, PbO source, order of the materials
addition, and presence of carbonates, on PbO-H2SO4 reaction. From this study, a mechanism is proposed for the reaction.
It explains why, by mixing PbO and H2SO4 in water, the tribasic lead sulfate cannot be obtained as a pure phase. Some
unreacted PbO always remains at the end of the reaction.

Introduction the mixing and curing operations. Indeed, a memory effect,

Although lead-acid batteries have been extensively used
for one century, there always exists some limitations to
their performances due to the low mass utilization at the
positive plate. Many improvements have been realized by
empirical approaches but there is a lack of fundamental
knowledge especially concerning the manufacture of flat
positive electrodes. This process involves the following
steps.
1. The oxidation of metallic Pb to lead oxide PbO
through processes called "Barton" or "mill" that produce
the "leady oxide" containing particles of aPbO and ~PbO
along with "free" lead.
2. The mixing of leady oxide in water with sulfuric acid
which results in a paste containing free lead, lead oxide,
and basic lead sulfates which are mainly 3PbO 9 PbSO~ 9
H20 (3BS) and 4PbO - PbSO4 (4BS) and, sometimes, acci-
dentally PbO - PbSO4 (1BS).
3. The pasting of the paste on lead alloy grids followed
by a flash drying.
4. The curing during which the pasted flat electrodes are
subjected to a treatment in a humid and hot atmosphere
(50-100~ depending on the manufacturing process). Dur-
ing this stage, the remaining metallic Pb is oxidized and the
basic lead sulfates recrystallize so that the plates exhibit
improved mechanical strength and better adherence of the
active material to the current collector.
5. The soaking and formation of the cured plates, a step
in which the plates are immersed in sulfuric acid and
electrochemically oxidized to ensure that the basic lead
sulfates are converted into the positive final active mate-
rial, PbO2.
Each one of these five steps influences the positive active
mass behavior during cycling. This is particularly true for
2710 J. Electrochem. Soc., Vol. 142, No. 8, August 1995 9 The Electrochemical Society, Inc.
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which could be related to the nature and the morphology of
the basic lead sulfate formed during the mixing and curing,
has been observed for the electrodes in cycling.l'2 For exam-
ple, plates obtained from 4BS-type pastes exhibit better
mechanical strength than the 3BS ones, but a complete
conversion of 4BS into PbO2 is difficult to achieve during
the final formation step. These facts are generally ascribed
to the morphology of the 4BS phase which tends to form
large needle-shaped crystals. However, since the exact
mechanisms involved during both the manufacture a n d cy-
cling operations are not yet well known, the cause of the
memory effect by the morphological features of the basic
lead sulfates has to be demonstrated. 1
Among the different transformations involved during the
electrode preparation, only the mechanism of the 4BS --->
PbO2 transformation has been clearly elucidated. This was
initially done by Burbank 3 and latter confirmed by several
authors. 4'~ The interlocking macrotexture of the 4BS large
needle-shaped crystals is retained after the formation; the
small PbO2 particles tend to form porous needle-shaped
agglomerates. This reaction was described by Burbank as a
metasomatic process. In a recent article, Lam gave addi-
tional results concerning the 4BS --~ PbSO4 --->P b Q and
4BS -4 PbO2 transformations occurring during the soak-
ing-formation stage. 6
For the other transformations involved during the prepa-
ration of the positive electrodes (PbO + H2SO4 ~-> 3BS;
PbO + H2SO4 --> 4BS; 3BS --~ PbO2) r/o clear mechanism can
be found in the literature. In the case where only tribasic
lead sulfate is produced by mixing, Iliev and Pavlov7 tried
to understand how the tribasic lead sulfate precipitation
proceeds. The interpretation of their results is rather diffi-
cult because they worked with industrial electrodes c o n -
 J. Electrochem. Soc., Vol. 142, No. 8, August 1995 © The Electrochemical Society, Inc. 2711

q
Fig. 1. SEM photographs of commercially available lead oxides:
(a, top left) red Merck (b, above) yellow Merck, and (c, left) Strem.

raining a lot of different phases ((~ and ~PbO, Pb, 3PbO • nisms were not studied in detail. In this paper, the mecha-
PbSO~ • H~O, 4PbO • PbSQ, ...) with a not well-defined nism of formation of tribasic lead sulfate is discussed on
morphology. Rajah 8 and later Davies and Wright 9 suggested the basis of the characterization results of the different
that a passivating layer of PbSQ was formed on the surface phases observed during the reaction. X-ray diffraction
of the PbO particles when sulfuric acid is added without (XRD), infrared (IR) spectroscopy, scanning and transmis-
giving clear evidence of this suggestion. In fact, most pa- sion electron microscopy (SEM and TEM) were used for
pers related to the mixing and curing steps are more this purpose. Moreover, the influence on the reaction of
devoted to the determination of the factors which influence several experimental parameters (composition of the start-
the nature of the prepared basic lead sulfate (mono-, tri-, or ing PbO + H2SO4 + H20 mixture, temperature, morphology
tetrabasic one) than to the mechanisms involved in the re- of the reactants and reaction atmosphere) is investigated.
action. Pavlov 1° has shown that the nature of basic lead
sulfate changes depending on the sulfuric acid density and
Experimental
Starting PbO precursors.--Three lead oxides were used
the temperature. For low densities (i.e., with H2SOjPbO
in this study, yellow Merck PbO, red Merck PbO, and Strem
ratio less than 6%) and high temperatures (over 60°C), the
PbO. Commercial yellow Merck lead oxide is orthorhombic
tetrabasic lead sulfate precipitates, while for higher densi- while red Merck oxide is tetragonal. Both compounds show
ties and lower temperatures, the precipitation of the triba-
sic or monobasic sulfate is favored. The PbO structural
modification (~ or ~) is thought to influence the nature of
the basic lead sulfate formed, but there are controversies
on this subjectY '11'12Some think that the ~ modifica-
tion (orthorhombic PbO) favors the tetrabasic lead sulfate
production ~'7while others claim that it is the c~ one (tetrag-
onal PbO). 11,12
This work is part of an extended study of the mechanisms
involved during manufacture and formation of the positive
flat plates. 13 It is focused on the formation of 3BS by mix-
ing. In the industrial process, leady oxide is generally
added in excess with a low water content in order to obtain
a paste with a suitable consistency to fill the lattice struc-
ture of the grid. We chose to operate in more dilute solu-
tions than in real battery manufacture. Indeed, this method
is useful for investigating the reaction mechanisms of PbO
in sulfuric acid solution: dilute solutions allow an energic
stirring so that a good homogeneity is achieved inside the
reaction flask. Such dilute media were used by others for
preparing the 3BS or the 4BS phases, 3'4'14but the mecha- Fig. 2. SEM photography of lead oxide after grinding.
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 2712 J. Electrochem. Soc., Vol. 142, No. 8, August 1995 9 The Electrochemical Society, Inc.
10 to 20 ~m edged octahedral particles (Fig. l a and b).
Strem PbO is a mixture of the two structural types (or-
thorhombic and tetragonal). Its particle morphology may
be described as platelets without a definite shape with a
mean size of 4 ~m (Fig. lc).
In order to improve the reactivity of the oxides, the three
starting materials were also subjected to a grinding in a
SPEX 8000 mixer mill during 20 min. The resulting ground
materials were then used as starting PbO for some experi-
ments. The grinding operation decreases the particle size
until about 1 to 2 ~m as shown in Fig. 2 b u t also changes the
structural type of PbO: orthorhombic PbO is partly con-
verted into the tetragonal phase and vice versa.
Mixing experiments.-- The mixing of the starting mate-
rials was carried out in a flask equipped with a mechanical
stirrer, a mercury thermoregulator, a pH electrode, and a
condenser.
First, many experiments were performed under various
conditions in order to study the following factors: (i) the
temperature, which varied between 5 to 60~ (if) the ratio
of PbO and H2SO4 (molar ratio: 3 < PbO/H2SO4 < 5); (iii) the
PbO precursor (Merck and Strem commercial lead oxides,
ground or not); (iv) the addition order of the starting mate-
rials, and (v) the adsorption of carbonates on reactants and
products: most of experiments were performed under air
but some of them under argon in order to avoid carbonation
of the solid phases.
For these experiments, the duration of the reaction was
fixed at least at 24 h, and no sample was removed during
the course of the reaction to be sure that a quasi-equi-
librium state is achieved.
In a second step, representative experiments were chosen
among the previously investigated ones to study the mech-
anism of the reaction. Typically, a suspension of ground
Strem PbO (5.95 g) was introduced in a dilute sulfuric acid
solution (1.88 g of 9N H2SO4 in 140.7 g of pure water) at
room temperature in air. The stirring was maintained for
24 h. Samples were periodically removed from the suspen-
sion and characterized.
Characterization techniques.-- The PbO precursors and
the solid phases obtained during or after mixing were char-
acterized by the following techniques. X-ray measure-
ments were carried out using a Philips 1050 0-20 goniome-
ter (back monochromator, CuKa). IR spectra were recorded
with a Nicollet 510 Fourier transform infrared (FTIR) spec-
trophotometer. The textural characterization of the sam-
ples was performed either by scanning electron microscopy
(Philips SEM 505) or transmission electron microscopy
(Philips STEM CM12). The solid phase identification by
x-ray diffraction was not easy due to the overlapping of a
n u m b e r of peaks belonging to 1BS, 3BS, 4BS, aPbO, and
~PbO. Moreover, different x-ray diagrams have been pro-
posed for the 3BS phases in the literature. 15'16Recently, we
have established a new one from a pure 3BS sample13: this
phase was used as a reference material in this study.
Influence of the Experimental Conditions
Influence of the temperature and composition.--The
temperature plays a predominant role on the reaction ki-
netics. If the temperature of the reaction is lower than 10~
x-ray diffraction analysis reveals the presence of pure PbO
even after several days of mixing; this indicates that the
rate of the reaction is too slow in this range of temperature.
Between 20 and 60~ the tribasic lead sulfate precipitates
but a mixture of phases, whose nature depends on the start-
ing composition, is obtained.
In order to study the influence of the starting composi-
tion of PbO + H2SQ + H20 mixtures, we varied the molar
ratio PbO/H2SO4 around the stoichiometric value, which is
four for the tribasic lead sulfate. Figure 3 shows the differ-
ent starting compositions used in our experiments. The
precipitation conditions corresponding to other reported
studies 3'4'1~ are also given on this diagram for comparison.
The x-ray study (Fig. 4 and 5) shows that the pure triba-
sic lead sulfate is never obtained no matter what the start-
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1BS
10
4BS
W 9
e
i 8
g 7
h
t 6
% 5
4
H
2 3
S 2
O BURBANK
4 1
BIAGETTI
0
0 20 40 60 80 100
weight % PbO
Fig. 3. On this diagram, the point (0,0) corresponds to 100% in
H20. Each of the three arrows corresponds to the stoichiometric
compositions in H2S04 and PbO for preparing each of the three basic
lead sulfates in a more or less dilute solution. It can be seen that
Burbank and Biagetti worked in more dilute conditions than Pavlov
and Dapo (areas delimited by two I I ). The different points marked
on this diagram show the various starting compositions we have
chosen for the preparation of the basic lead sulfates.
ing composition is. If the composition corresponds to a
point located above the tribasic lead sulfate straight line
(see Fig. 3), tribasic and monobasic lead sulfates precipi-
tate sometimes with a small quantity of PbO remaining
(Fig. 4a). Below the tribasic straight line, PbO is present in
large amounts with 3BS (Fig. 4b). On the straight line, i.e.,
with the stoichiometric composition, some unreacted PbO
always remains along with 3BS (Fig. 5a), as evidenced by
the comparison with a reference 3BS sample (Fig. 5b). The
presence of unreacted PbO is not pointed out in the other
studiesY As mentioned in the experimental part, it is rela-
tively difficult to identify all the solid phases in the paste
due to several phenomena (overlapping peaks, confused x-
ray data for the 3BS phase, etc.).
PbO source infIuence.--In order to determine if the pres-
ence of unreacted PbO after mixing could be related to the
reactivity of the starting lead oxide, the influence of the
morphological features of the available lead oxides (Strem,
yellow Merck, and red Merck before and after grinding)
was compared.
No difference was noticed in the composition of the final
mixed product with the different lead oxides, even after
grinding. Mixtures of 3BS and PbO with the two structural
types were prepared in all cases. Moreover, no influence of
the PbO type could be found. The morphology was only
found to influence the reaction kinetics. The change in the
suspension coloration (from yellow-orange to white) indi-
cating the precipitation of the 3BS phase occurs more
rapidly for smaller particles. The coloration was used to
measure the reaction time which appears to strongly de-
pend on the mean size of the PbO particles.
Influence of order of materials addition.--The order of
materials addition was altered as follows: (i) sulfuric acid
 J. Electrochem. Soc., Vol. 142, No. 8, August 1995 9 The Electrochemical Society, Inc. 2713

was added to a suspension of PbO in water; (ii) PbO was o PbO

added to a mixture of water and sulfuric acid; and (iii) PbO
was added to acidified water (pH 2), and the remaining
sulfuric acid was then allowed to react.
In all the above cases, mixtures of 3BS with PbO and/or
1BS were identified by x-ray diffraction.
Influence of carbonates presence.--The IR spectra of the
3BS phase (Fig. 6) shows several bands due to sulfate ions
at 1130, 1095, 1033, 960, and 600 cm -1. Three peaks at 473,
446, and 411 cm -~ may be ascribed to the Pb-O vibration
modes. The narrow b a n d at 3570 cm -~ is probably due to
hydroxyl groups of water molecules H-bonded to sulfates 10 15 20 25 30 35 28
ions. Besides these SO4, O-H, and Pb-O bands, two peaks at
1400 and 700 cm -1, which are due to carbonate ions, clearly
appear in the spectra even if mixing is performed under an
argon atmosphere. Carbonation of samples is then very dif-
ficult to avoid. The fact that the peak at 1400 cm -~ is a
singlet indicates that these ions exhibit the D3h symmetry.
This means that the carbonate ions in our samples are
rather free t h a n coordinated to metallic cations. For coor-
dinated carbonates, the corresponding symmetries (Cs or
C2v) of these structures involve the splitting of the D3h de-
generate modes leading to a doublet peak in the 1300 to
1500 cm -1 range. Actually, there are two different types of
- - i . . . . . . 9 . . . . . . . . . 9 . . . . . . l - i . . . . s . . . . . .

10 1s 20 zs 30 35 20
o PbO
9 3BS Fi9. 5. X-Ray study of the final product vs. the starting composition
in PbO and H2S04. (a, top) When the starting composition is the
~IBS staichiometric one far 3BS, we obtain a mixture of 3BS and PbO. (b,
bottom) For comparison, here is the diagram of pure tribasic lead
sulfate.

carbonation for powder lead compounds. The carbonate

species can be adsorbed on the surface of the products be-
cause of the small size of the particles. This adsorption can
o occur during the grinding of the starting material or during
the drying of the final powder so that even if the experi-
ments are made under argon the final product can be car-
9 9 | bonated. However, adsorbed carbonates are generally coor-
|

/,/
w, 9
dinated to metallic ions: .they show the C2v symmetry with
the doublet peak between 1300 and 1500 cm -1. 18As the D3h
symmetry seems to predominate in our spectra, another
form of carbonation has to be considered. In water or in
8 t2 i6 20 24 28 32 36 humid air containing carbon dioxide, a small amount of
2e PbO or 3BS can be partly dissolved and converted into lead
carbonate phases (hydrocerussite or plumbonacrite) con-
~ PbO taining carbonate ions in the D3h symmetry. However, the
9 3BS amount of these carbonate compounds is often too small to
be identified on the x-ray patterns. By contrast, IR spec-
troscopy reveals the presence of these compounds as sur-
face phenomena are enhanced by this technique. It is also
possible to identify a few hexagonal particles of lead car-
bonate by TEM (Fig. 7). In fact, our starting lead oxides,

9 v(c03-)
1~(S04Z-)
o 40
o_
tq

3o
m
~- Pbo)
20

_j 8 t2 t6 20 24 28 32 36
10
211
Fig. 4. X-Ray study of the final product vs. the starting composition 3500 3000 2S00 2000 1500 1000 500
in PbO and H2S04. (a, top) When Ihe starting composition is too rich Wavelength (crn-1)
in H2S04 compared to the stoichiometric composition for 3BS,
the prepared mixture is "3BS + 1BS + PbO." (b, bottom) When the Fig. 6. Infrared spectroscopy diagram of the powders after mixing.
starting composition is too rich in PbO, the final mixture is "3BS + The sulfate and carbonate bonds are indexed. The vibrations due to
PbO." PbO and H20 can he seen, too.
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 2714 J. Electrochem. Soc., Vol. 142, No. 8, August 1995 9 The Electrochemical Society, Inc.
Fig. 7. TEM photography of
lead carbonate.
before mixing, always contain more or less lead carbonates
depending on the storing conditions (duration and hy-
grometry). The carbonation cannot then be avoided even
under argon atmosphere.
In short, from the investigation of a lot of experimental
conditions, it appears that some unreacted PbO always re-
mains along with the 3BS phase during mixing. This means
that the reaction cannot be complete using this method. In
the following section, a possible explanation is given from
the study of the reaction mechanism.
Study of the ReactionMechanism
Characterization of the solid phases during the course of
the reaction.-- In order to understand better how the 3BS
phase forms, samples were taken from the mixture during
the course of the reaction and studied by x - r a y diffraction
and SEM (see Experimental section). Simultaneously, the
pH curves were recorded during the reaction.
The pH curve typically obtained at 20~ is shown in
Fig. 8. Similar curves are obtained at higher temperatures.
Two parts can be distinguished in this curve. In a first
stage, the p H rapidly increases indicating that the rate of
reaction is relatively high. In the second stage, the pH is
pH=f(t) ~, 20~
10
~ f
8
6 ~IBS
pH
4
2 &
0 I I I ~ I
20 40 60 80 100
temps (rain)
Fig. 8. pH curve typically obtained at 20~ during the mixing of
PbO, H2S04, and H20.
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nearly stabilized and reaches a pseudo plateau: the reac-
tion then becomes very slow.
Samples taken in the first part of the curve contain
mainly P b S Q , PbO, and ]BS, but also 3BS in a very small
amount (Fig. 9). This indicates that PbSO4 and monobasic
lead sulfate are intermediate species in the reaction. Scan-
ning electron micrographs of such samples (Fig. 10a) re-
vealed the presence of three types of particles: (i) squared
particles, which ca n be easily identified as PbSO4 particles
by comparison with micrographs of a pure PbSO4 powder;
(it) needles, which are generally observed for the 1BS and
3BS phases; and (iii) agglomerates of small particles, which
probably correspond to the PbO phase.
Samples taken in the second part of the curve contain the
3BS phase along with small amount of PbO. The 1BS and
PbSO4 phases are not identified in the mixture at this stage
of the reaction. The corresponding SEM micrographs show
agglomerates of small particles and needles (Fig. 10b). The
needles, sometimes broken, can also be observed by TEM
(Fig. 11). The corresponding selected area electron diffrac-
tion (SAED) patterns clearly indicate that these needles are
due to the tribasic lead sulfate phase. The identification of
the agglomerates of small particles is not possible because
SAED spots cannot be indexed with accuracy due to the
large number of crystallites. Such agglomerates may corre-
spond to PbO. However, it seems hard to attribute them
only to PbO in view of their large number compared with
the small amount of PbO detected by x - r a y diffraction
(Fig. 3a). The 3BS phase probably crystallizes in two differ-
ent ways leading to two types of morphology: needles
(about 5 ~m in length and 1 ~m in thickness) and micronic
particles without a definite shape.
o PbO
+PbS04
*3BS
+
1
120
+ + I :J,
10 1S 20 25 30 35 20
Fig. 9. X-RoydiffTocfion pattern of samples taken at the start of the
mixing, in the first port of the pH curve (pH < 8).
 J. Electrochem. Soc., Vol. 142, No. 8, August 1995 9 The Electrochemical Society, Inc.
Discussion
The study of the pH and of the nature of the solid phases
during the course of mixing clearly suggests that the reac-
tion of PbO with H2SO4 proceeds in two steps.
During the first step, which is the most rapid, as clearly
indicated by the pH curve, the lead sulfate PbSO, is prefer-
entially formed. The change in the morphology of the solid
particles (agglomerates of pellets for the PbO starting
product/squared monocrystalline particles for the PbSO~
phase formed at this stage) indicates that the reaction oc-
curs via the solution. The concentration of the different
species in solution and the low pH values at the beginning
of the reaction allow the nucleation and growth of the lead
sulfate from the solution. PbO dissolves and dissociates in
the acidic solution. This reaction produces Pb 2§ and OH-
ions. These hydroxide ions react and neutralize the H30 §
species in the solution so that the pH increases. It may be
concluded that the chemical reactions that prevail in this
first step are
PbO + H20 -e Pb 2§ + 2 0 H -
Pb 2§ + SO~ --~ PbSO4
2 O H - + 2H* ~ 2H20
However, mono- and tribasic lead sulfates begin to precipi-
tate in very small amounts during this stage.
The second step of the reaction is slower as the pseudo-
plateau is achieved when the pH value becomes 8 or more.
For such values of pH, PbO is rather stable but intermedi-
ate reaction products, PbSO4 and PbO 9 PbSO4 progres-
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2715
Fig. 10. SEM photographs:
(a, left) of the samples taken in
the first part of the pH curve and
(b, right) of the final product.
Fig. 11. TEM photography of
the needles of 3BS and corre-
sponding electron diffraction
pattern.
sively disappear as shown by x-ray diffraction due to their
dissolution
PbSO4 --+ Pb 2§ + SO4
PbO 9PbSO4 + H20 --~ 2Pb 2+ + SO4 + 2 OH
Simultaneously, 3BS forms by consuming Pb 2+species from
the solution
4Pb 2§ + SO4 + 6 OH- -~ 3PbO 9PbSO4 - H20 + 2H20
Hence, the Concentration of Pb 2§ in the solution during
the second step remains relatively low, It is probably not
high enough to permit an homogeneous nucleation of the
3BS phase. Homogeneous nucleation would occur if an
oversaturation of the Pb ~§species was achieved in the solu-
tion so that nuclei of the 3BS solid phase formed in the
solution. The increasing amount of 3BS in the mixture dur-
ing the second step can probably be explained as follows.
There is heterogeneous nucleation of tribasic lead sulfate
on the surface of solid germs and then growth from the
solution. These solid germs could be either PbSO4, PbO -
PbSO4, or PbO particles. However, the germination of the
tribasic lead sulfate seems to be more probable at the sur-
face of PbO and PbO 9PbSO4 particles as: (i) the morphol-
ogy of the 3BS final particles seems to derive from that of
PbO (micronic particles without definite shape) or PbO -
PbSO, (needles) but not from that of PbSO~ (no squared
particles at the end of reaction) and (it) the local pH at
the surface of PbO and PbO 9 PbSO4 particles is more
basic than for PbSO4 and favors the nucleation of tribasic
lead sulfate.
 2716 J. Electrochem. Soc., Vol. 142, No. 8, August 1995 9 The Electrochemical Society, Inc.
Such a mechanism may explain why there always re-
mains some unreacted PbO even when the starting condi-
tions are the best ones for producing the tribasic lead sul-
fate (stoichiometric composition and temperature between
20 and 60~ During the second step of the reaction, the
dissolution of PbO becomes negligible and the nucleation
of 3BS mainly occurs on the surface of the remaining p a r t i -
cles of PbO. At the end of the reaction, the oxide particles
are isolated from the solution by a layer of tribasic lead
sulfate that prevents them from reacting with SO~- ions in
the solution. The diffusion of SO 2- species across this
sheet until PbO becomes the limiting step regarding to the
kinetic.
Conclusion
By mixing PbO, H2SO4, and H20 in dilute solutions, the
tribasic lead sulfate is mainly obtained if the starting com-
position is the stoichiometric one. However, the carbona-
tion of the produced material is hard to avoid, and the
reaction is not complete. Actually, there still remains unre-
acted PbO. The study of the mechanism of the reaction has
shown that this reaction is kinetlcally governed. In fact, the
coating of PbO particles by the tribasic lead sulfate makes
the diffusion of SO~- species across the sheet very difficult
and prevents them from reacting with PbO.
In the industrial conditions, there is an excess of PbO
which leads the starting composition to be in the tetrabasic
lead sulfate zone. As the reaction is carried out below 60~
the tetrabasic lead sulfate does not precipitate. So, at the
end of the reaction the tribasic lead sulfate is not single
phase but contaminated by PbO in a larger amount that we
experimented with our laboratory process.
In order to prepare the pure tribasic lead sulfate, some
other methods have to be used. These studies are the sub-
ject of an other publication, z~The study of the curing of the
pure tribasic lead sulfate is now being developed in the
laboratory.
Acknowledgments
The authors would like to thank the ADEME (Agence de
l'Environnement et de la Maitrise de l'Energie) and the
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CEAC company for their financial support and fruitful
discussions.
Manuscript submitted Dec. 29, 1994; revised manuscript
received March 22, 1995.
Universitd de Picardie Jules Verne assisted in meeting the
publication costs of this article.
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