Journal of Power Sources 137 (2004) 288–308

Influence of H2 SO4 concentration on the mechanism of the processes and

on the electrochemical activity of the Pb/PbO2 /PbSO4 electrode
D. Pavlov∗ , A. Kirchev, M. Stoycheva, B. Monahov
Lead-Acid Batteries Department, Institute of Electrochemistry and Energy Systems (former CLEPS),
Bulgarian Academy of Sciences, Sofia 1113, Bulgaria
Received 25 February 2004; received in revised form 6 May 2004; accepted 7 June 2004
Available online 31 July 2004

Abstract

The aim of the present investigation is to study the influence of H2 SO4 concentration on the electrochemical activity, the phase composition
and the structure and morphology of the PbO2 particles. The study is performed through cycling (between 700 and 1600 mV versus
Hg/Hg2 SO4 electrode) of a Pb/PbO2 /PbSO4 electrode immersed in sulfuric acid solutions of various concentrations (ranging within 2
orders of magnitude: 6.0–0.05 M H2 SO4 ). In this concentration region, sulfuric acid dissociates in two steps resulting in the formation of
HSO4 − and SO4 2− ions, respectively. It has been established experimentally that the electrochemical activity of the PbO2 /PbSO4 electrode
depends on the concentration of HSO4 − ions in the solution. Three acid concentration regions can be distinguished: (a) active acid
concentration region (5.0 M > CH2 SO4 > 0.5 M), where the concentration of HSO4 − ions is the highest and a ␤PbO2 phase is formed; PbO2
particles are drop-like in shape and contain large hydrated (gel) zones; the electrode has the highest capacity; (b) passive high concentration
region (CH2 SO4 > 5.0 M), where the concentration of HSO4 − ions decreases at the expense of formation of H2 SO4 molecules; crystal-shaped
␣PbO2 particles are formed; the capacity of the electrode declines; (c) passive low concentration region (CH2 SO4 < 0.5 M), where the
concentration of HSO4 − ions decreases at the expense of the formation of SO4 2− ions; the content of ␣PbO2 in the anodic layer increases;
PbO2 particles are crystal-shaped and are interconnected in dendrites; the capacity of the electrode declines. The above electrochemical
behavior of the PbO2 /PbSO4 electrode is explained by the mechanism of the reactions in the gel zones of the PbO2 particles and by the
influence of HSO4 − ions on the number of electrochemically active particles. On grounds of the obtained experimental results it has been
established that the working interval within which the CH2 SO4 may change on cycling is from 5.0 to 1.5 M, i.e. 3.5 M H2 SO4 per 1 l of
H2 SO4 solution with s.g. 1.28 takes part in the reactions on both battery plates. This is the maximum amount of H2 SO4 in the solution that
would have no detrimental effect on the positive plates of the lead-acid battery.
© 2004 Elsevier B.V. All rights reserved.

Keywords: PbO2 /PbSO4 electrode; PbO2 reduction; PbSO4 oxidation; PbO2 structure; Lead-acid batteries; Lead-acid batteries charge processes; Lead-acid
batteries discharge processes

1. Introduction particles and agglomerates formed during charge as well

as the morphology of the PbSO4 crystals obtained during
The cycle life of lead-acid batteries is often limited by discharge [1–6].
softening, shedding and passivation of the lead dioxide active Valve-regulated lead-acid batteries operate under condi-
mass. The positive active material (PAM) is a porous mass. tions of slight deficiency of H2 SO4 as a result of which, on
On battery cycling, reactions proceed as a result of which the deep discharge, the concentration of the H2 SO4 in the plate
H2 SO4 concentration in the PAM pores increases on charge pores drops down to very low values and the subsequent
and decreases on discharge. charge starts at this low concentration. On the other hand,
in an attempt to compensate partially for the H2 SO4 short-
PbO2 + H2 SO4 + 2H+ + 2e− ⇔ PbSO4 + 2H2 O (1)
age, many VRLA battery manufacturers use H2 SO4 solu-
These changes in H2 SO4 concentration in the pores of PAM tions with concentrations higher than 1.28 s.g. At the end of
may affect both the structure and morphology of the PbO2 charge the H2 SO4 concentration in the plate pores is even
higher than that of the solution initially filled into the bat-
∗ Corresponding author. Tel.: +359 2 718651; fax: +359 2 731552. tery. The question arises whether these extreme variations of
E-mail address: [email protected] (D. Pavlov). the H2 SO4 concentration in VRLAB allow the formation of

0378-7753/$ – see front matter © 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jpowsour.2004.06.006
 D. Pavlov et al. / Journal of Power Sources 137 (2004) 288–308 289

PbO2 and PbSO4 structures with high chemical and electro- paper. At magnifications higher than 40,000, we observed
chemical activity, which would yield high battery capacity the PbO2 particles and PbSO4 nuclei (microstructure), and at
and long cycle life. lower magnifications, the interconnection of PbO2 particles
The processes of formation of the PbO2 and PbSO4 in agglomerates and aggregates (macrostructure).
phases are complicated first by the two dissociation stages
of H2 SO4 , which lead to formation of SO4 2− and HSO4 − 2.2. Electrochemical cell and experimental set-up
ions. Secondly, the solubility of PbSO4 crystals depends
strongly on the H2 SO4 concentration, which is responsible A classical three-electrode glass cell was used comprising
for the different concentration of Pb2+ ions in the pores of a smooth Pb (99.999%) working electrode, a Hg/Hg2 SO4
PAM depending on the state of charge and discharge [7,8]. reference electrode and a Pt counter-electrode. The anodic
Still another peculiarity is that the sulfuric acid ions adsorb layer was obtained through cycling of the Pb electrode
onto the PbO2 surface and thus influence the processes immersed in H2 SO4 solution. Electrode polarization was
of PbO2 phase formation [9–11]. And finally, Pb2+ ions conducted between 1600 and 700 mV (versus Hg/Hg2 SO4
form a number of complex ions depending on the pH of electrode), i.e. within the PbO2 and PbSO4 potential re-
the solution [12]. It has been established that the H2 SO4 gions, at a scan rate of 100 mV/s. This technology allowed
concentration affects not only the electrode kinetics but gradual formation of a PbO2 anodic layer in the H2 SO4 so-
also the maximum utilization of the active materials of the lution of a given concentration. After 1 or 16 h of cycling,
Pb/PbO2 /PbSO4 electrode [13–17]. the electrode was taken out of the solution and samples
The processes of PbSO4 oxidation to PbO2 and of PbO2 of the obtained anodic layer were examined in a scanning
reduction to PbSO4 involve the decomposition of one solid electron microscope. Its phase composition was determined
phase and the formation of a new solid phase. To disclose through X-ray diffraction analysis.
the relationship between the processes of decomposition of Table 1 summarizes the values for the H2 SO4 concentra-
the initial phase and those of formation of the new phase tions, as expressed in the chemical practice (M, mol/l) and
is one of the aims of the present paper. The second aim in the battery industry (s.g.: specific gravity), respectively.
is to determine the influence of H2 SO4 concentration on Merck’s data tables were used [18]. A more detailed descrip-
the above processes. And finally, based on the fundamen- tion of the procedures used is presented in reference [6].
tal results obtained, to draw a purely practical conclusion
about the amount of H2 SO4 that can be utilized during
2.3. Dependence of the equilibrium potential of the
cycling with no adverse effect on the cycle life of the
Pb/PbO2 /PbSO4 electrode on H2 SO4 concentration
battery.
For H2 SO4 concentrations higher than 0.5 M (pH < 1.0)
the equilibrium potential of the Pb/PbO2 /PbSO4 electrode
2. Experimental methods
can be represented by the following equation [19]:
2.1. Philosophy of the investigation PbO2 + HSO− + −
4 + 3H + 2e = PbSO4 + 2H2 O (2)

The mechanism of the processes of conversion of one E = 1.628 − 0.88 pH + 0.029 log aHSO4 − (2 )
solid phase into another one as a result of an electrochemi-
cal reaction can be disclosed if the electrochemical reaction The potential is referred to a hydrogen electrode. The
proceeds at a high rate. In this case, some of the slow el- equilibrium potential of the Pb/PbO2 /PbSO4 electrode de-
ementary processes will not proceed at all and the individ- pends on the pH of the H2 SO4 solution. On varying the
ual elementary reactions and the formation of intermediate H2 SO4 concentration from 5.0 to 0.05 M, the equilibrium
products could be differentiated. The subsequent slow poten- potential shifts from 1258 to 787 mV (versus Hg/Hg2 SO4
tial sweep provides information about the slow processes. In electrode). When cycled between 1600 and 700 mV the elec-
the present investigation we used linear scanning voltametry trodes stay in the PbO2 and PbSO4 potential regions differ-
(LSV) at potential scan rate of 100 mV/s for the fast poten- ent periods of time as a result of which different amounts of
tial sweep and 2.0, 4.0 or 10.0 mV/s for the slow one. PbO2 and PbSO4 phases are formed. In concentrated H2 SO4
We used sulfuric acid solutions with concentrations from solutions the time of stay of the electrode in the PbSO4 po-
6.0 to 0.05 M H2 SO4 , i.e. the CH2 SO4 was varied within 2 tential region will be longer than in the PbO2 one, whereas at
orders of magnitude. low H2 SO4 concentrations the reverse situation is observed.
Based on the structure of the anodic layer formed and The aim of the present investigation is to establish whether
the morphology of the particles we can judge about the the changes in H2 SO4 concentration lead to changes in the
processes of nucleation and growth of the new phase as type and structure of the anodic layer, and in the morphol-
well as about the decomposition of the initial phase. For ogy of the PbO2 particles and their electrochemical activ-
the purpose we performed exhaustive SEM examinations ity, as well as in the morphology of the PbSO4 crystals, i.e.
and the characteristic SEM pictures are presented in this purely qualitative changes.
290 D. Pavlov et al. / Journal of Power Sources 137 (2004) 288–308

Table 1
H2 SO4 concentrations of the solutions used for the experiments [18]
M (mol/l) 6.0 5.0 2.81 2.06 1.56 0.86 0.5 0.18 0.05
Specific gravity of H2 SO4 1.39 1.285 1.17 1.125 1.095 1.050 1.030 1.010 1.000
C (%) 44.17 37.95 23.95 18.09 14.04 7.704 4.756 1.731 0.49

3. Experimental results within this concentration region has low electrochemi-

cal activity that decreases with decrease of the H2 SO4
3.1. Dependence of the amount of PbO2 involved concentration.
in the electrochemical reaction of reduction at the
Pb/PbO2 /PbSO4 electrode on H2 SO4 concentration 3.2. Phase composition of the anodic layer formed at
(electrochemical activity of PbO2 ) various H2 SO4 concentrations

The amount of PbO2 in the anodic layer that takes part The phase composition was determined through XRD
in the electrochemical reduction was measured coulometri- analysis, from the areas of the characteristic diffraction
cally and the results obtained were presented in the first an- peaks for ␤PbO2 (d = 0.350 nm), ␣PbO2 + tetPbO (d
nouncement of these investigations [6]. The present paper = 0.313 nm—this line is common for both phases, but it re-
provides some additional results. Fig. 1 presents the depen- flects mainly the content of ␣PbO2 ), PbSO4 (d = 0.300 nm)
dence of the electrochemical activity of PbO2 (determined and Pb (d = 0.284 nm). The X-ray patterns give the phase
by the quantity of electricity flowing through the electrode on composition of the surface sub-layer of the anodic layer
reduction of the PbO2 layer at cathodic scan rate of 1 mV/s) that is in contact with the solution and this sub-layer was
on the H2 SO4 concentration. The measurements were per- examined by scanning electron microscopy.
formed after 1 and 16 h of electrode cycling. Judging by the Fig. 2 presents the areas of the characteristic X-ray diffrac-
profile of the curves, three H2 SO4 concentration regions can tion peaks reflecting the content of the individual crystal
be identified: phases for the anodic layers formed in H2 SO4 solutions
(a) Passive high concentration region: This region includes
concentrations higher than 5 M H2 SO4 . The anodic layer 3500
PR AR PR
formed within this region has low electrochemical ac- 3000
tivity that decreases on further increase of the H2 SO4
Peak area / counts

concentration. 2500
β-PbO2
(b) Active medium concentration region: Covering concen- 2000
trations between 5.0 and 0.5 M H2 SO4 and yielding an
1500
electrochemically active anodic layer. It is within this
concentration region that the positive electrode of the 1000
lead-acid battery operates. α -PbO2
500
(c) Passive low concentration region: It includes concen- 1h PbSO 4
trations below 0.5 M H2 SO4 . The anodic layer formed 0
0,01 0,1 1 10
(A) MH2SO4 / mol.l-1

6 3500
Active H2SO4
PR AR PR
concentration
5 region
3000

2500
Peak area / counts

4
q / C.cm -2

2000 β-PbO2
16 h
3
1500

2 PbSO4
1000
α-PbO2
500
1 16 h
1h
0
0 0,01 0,1 1 10
0,01 0,1 1 10 (B) MH2SO4 / mol.l-1
MH2SO4 / mol.l-1
Fig. 2. Phase composition of the anodic layer formed for 1 h (a) and
Fig. 1. Amount of active PbO2 involved in the reduction process, as a for 16 h of cycling (b) of a Pb electrode between 700 and 1600 mV at
function of H2 SO4 concentration [6]. 100 mV/s vs. H2 SO4 concentration.
 D. Pavlov et al. / Journal of Power Sources 137 (2004) 288–308 291

MH2SO4 / m ol.l-1 its maximum value, 6.0–6.5 mg/l. On further decrease of

1,65 3,39 5,26 7,21 9,20 11,27
the H2 SO4 concentration the solubility of PbSO4 decreases
8 again.
On comparing Figs. 1–3 it can be seen that the solubility
7
Active
Passive region
of PbSO4 is the highest within the active zone of H2 SO4
6 region
concentrations. The maximum amount of ␤PbO2 formed in
SPbSO4 / m g.l-1

5 the anodic layer at 0.86 M H2 SO4 concentration corresponds

Danel and Plichon to the maximum solubility of the PbSO4 crystals. In the
4
Vinal and Craig passive zones of H2 SO4 concentrations, PbSO4 has but a low
3 solubility, different in concentrated and diluted solutions.
2

1 3.4. Basic elements comprising the structure of the lead

PbSO4 solubility
0
dioxide layer
1 1,1 1,2 1,3 1,4 1,5 1,6
CH2SO4 / s.g. When a lead electrode immersed in H2 SO4 solution is po-
larized in the lead dioxide potential region (ϕ > equilibrium
Fig. 3. Dependence of the solubility of PbSO4 crystals on H2 SO4 concen- potential of the Pb/PbO2 /PbSO4 electrode), the surface of
tration, as determined by Vinal and Craig [7], and Danel and Plichon [8].
the electrode is oxidized and a PbO2 layer is formed. Let us
call this layer primary PbO2 layer.
On cycling, when the electrode potential becomes more
with concentrations varying between 6.0 and 0.05 M after
negative than the equilibrium potential of the Pb/PbO2 /
1 h (Fig. 2a) and 16 h (Fig. 2b) of cycling.
PbSO4 electrode system, the primary layer is reduced to
It is evident from Fig. 2a that, within the passive high
PbSO4 . Then during the anodic sweep, when the potential
concentration region CH2 SO4 > 5.0 M H2 SO4 ), the anodic
enters again the lead dioxide potential region, the PbSO4 is
layer contains mostly ␣PbO2 and PbSO4 , and negligible
oxidized to PbO2 . The secondary PbO2 layer is formed.
amounts of ␤PbO2 .
Fig. 4 shows the elements building the structure of the
In the active H2 SO4 concentration region the amount of
anodic layer. These include:
␤PbO2 in the anodic layer exceeds by several times that of
the ␣PbO2 phase. Below 0.86 M H2 SO4 concentrations, the (a) Individual particles (Fig. 4a): These particles are globu-
content of ␤PbO2 decreases on further dilution of the H2 SO4 lar in shape. Most of the globules have almost spherical
solution. shape and some of them are elongated.
In the passive region of low H2 SO4 concentrations (b) Agglomerates (Fig. 4a and b): Several particles (10–15)
(CH2 SO4 < 0.5 M), the amount of ␣PbO2 in the anodic layer interconnect to form an agglomerate. Agglomerates may
increases, whereas that of ␤PbO2 decreases. The reactions be almost spherical, elongated or shapeless. The con-
of ␣PbO2 reduction to PbSO4 and the subsequent oxidation nections between the particles may vary from tightly
to ␤PbO2 are impeded. It is true that at these concentrations adhering to each other with hardly visible inter-particle
the electrode stays for a very short time within the PbSO4 boundaries to well pronounced particles with clearly vis-
potential region, which may have its own effect on phase ible small contact surfaces between them.
composition, too. (c) Aggregates (Fig. 4b): Numerous agglomerates and par-
Comparing the data for the two passive regions it is worth ticles interconnect to form aggregates. The latter may
noticing that great amounts of ␣PbO2 form in both regions. be shapeless and microporous in structure.
In the active region mainly ␤PbO2 is formed. A compari-
son between Figs. 1 and 2 suggests that the morphology of These are the basic elements building the structure of the
the PbO2 crystals exerts an influence on its electrochemical anodic layer formed on oxidation of a smooth electrode. An
activity. analogous structure has been established also in the positive
active mass [20,21]. In fact, through cycling the Pb electrode
3.3. Solubility of PbSO4 crystals as a function of H2 SO4 for 1 or 16 h we form positive active mass by the Gaston
concentration Planté method.

Fig. 3 presents the dependence of the solubility of PbSO4 3.5. Structure of the anodic layer formed in the passive
crystals on the concentration of H2 SO4 as determined by high acid concentration region
Vinal and Craig [7], and Danel and Plichon [8].
In 5.0 M H2 SO4 solution, the solubility of PbSO4 crys- (a) 5 M H2 SO4 solution (1.28 s.g.): The SEM pictures in
tals is low, about 1.8 mg/l. It almost doubles (4.1 mg/l) in Fig. 5 show the anodic layer after 1 h of electrode cy-
2.81 M H2 SO4 solution and in the concentration region be- cling, whereby electrode polarization was stopped at
tween 2.06 and 0.5 M H2 SO4 the PbSO4 solubility reaches 1600 mV. The pictures feature:
292 D. Pavlov et al. / Journal of Power Sources 137 (2004) 288–308

Fig. 4. Building elements of the structure of the PbO2 anodic layer.

• Zones of compact continuous passive layer compris- in the cycling processes and probably contain ␤PbO2
ing tightly interconnected almost spherical PbO2 par- particles.
ticles with no pores in-between (Fig. 5a); These zones
have probably formed during the initial anodic oxida- The anodic layers obtained after 1 and 16 h of cycling
tion of lead and they present the primary anodic layer. do not differ much in structure, except for the increased
This layer is passive and participates but weakly in size of the zones of loose structure on continuous elec-
the charge–discharge processes. trode cycling.
• Zones of loose structure with well shaped PbO2 par- Fig. 6 presents pictures of the anodic layer formed
ticles and micropores between some of the particles after 1 h of cycling of the electrode whose cathodic
(Fig. 5b); These zones in the anodic layer are involved polarization was stopped at 700 mV, i.e. in the PbSO4

Fig. 5. Anodic layer formed after 1 h of cycling of a Pb/PbO2 /PbSO4 electrode in 5 M H2 SO4 solution. Electrode polarization was stopped at 1600 mV
vs. Hg/Hg2 SO4 reference electrode.
 D. Pavlov et al. / Journal of Power Sources 137 (2004) 288–308 293

these active centers will have different activity on PbO2

reduction.
(b) 6 M H2 SO4 solution (1.34 s.g.): Fig. 7 presents SEM
micrographs of the anodic layer formed after 1 h of
electrode cycling, whereby the polarization was stopped
at 1600 mV. Crystal-shaped PbO2 particles of two
sizes are observed: (i) 80–100 nm, and (ii) larger than
150–200 nm. The PbO2 particles cover uniformly the
lead surface. Small aggregates of crystal-shaped well
differentiated PbO2 particles (80-100 nm) can be seen
here and there (Fig. 7a). Probably, these have formed as
a result of oxidation of the PbSO4 crystals, whereby the
obtained aggregates have not preserved fully the matrix
of the PbSO4 crystals. On comparing Figs. 5b and 7b it
can be seen that in 5 M H2 SO4 solution the PbO2 par-
ticles are round or oval in shape, whereas those formed
in 6 M H2 SO4 solution have crystal shapes.
Fig. 8 shows pictures of the anodic layer formed after
16 h of electrode cycling in 6 M H2 SO4 solution, whereby
the polarization was stopped at 1600 mV (Fig. 8a and b)
or at 700 mV (Fig. 8c and d). At this acid concentration,
Fig. 6. Anodic layer formed after 1 h of cycling of a Pb/PbO2 /PbSO4 the reduction of PbO2 particles yields flat prismatic PbSO4
electrode in 5 M H2 SO4 solution. Polarization was stopped at 700 mV, crystals with well shaped walls, edges and apexes (Fig. 8d).
whereby part of the PbO2 has been reduced and PbSO4 nuclei and crystals Part of these crystals remains unoxidized for the short
have formed.
time of stay of the electrode within the PbO2 potential
region (Fig. 8b). The low solubility of the PbSO4 crystals
potential region. PbSO4 nuclei (sized between 80 and contributes, too. The XRD analysis of the anodic layer
150 nm) and PbSO4 crystals (about 1 ␮m) had formed formed on the electrode when its polarization was stopped
at some sites on the PbO2 surface. This indicates that at 1600 mV (Fig. 2) indicates that it is composed mainly
the reduction of PbO2 proceeds in active centers. As of ␣PbO2 and contains considerable amounts of PbSO4
the PbSO4 nuclei differ in size, it may be expected that crystals and very small amounts of ␤PbO2 . An interesting

Fig. 7. Structure of the anodic layer formed after 1 h of cycling of a Pb/PbO2 /PbSO4 electrode in 6 M H2 SO4 solution. Electrode polarization was stopped
at 1600 mV.
294 D. Pavlov et al. / Journal of Power Sources 137 (2004) 288–308

Fig. 8. Macro (a and c) and microstructure (b and d) of the anodic layer formed after 16 h of cycling of a Pb/PbO2 /PbSO4 electrode in 6 M H2 SO4
solution. Electrode polarization was stopped at: 1600 mV (a and b) and 700 mV (c and d).

finding is that the ␣PbO2 phase is formed in strongly acidic time depends on the response time of the potentiostat. Dur-
medium and its particles have well pronounced crystal ing this period, a very strong current flows through the
shapes. electrode determined by the first electrochemical reaction of
Pb oxidation to Pb2+ . A passive layer of PbSO4 is formed.
3.6. Cycling of Pb electrodes in the active H2 SO4 Then the potential increases rapidly and exceeds the equi-
concentration region librium potential of the Pb/PbO2 /PbSO4 electrode. The
PbSO4 layer is oxidized to PbO2 . The processes involved
After switching on the potentiostat a certain time is in the oxidation have been discussed earlier [22,23]. The
needed for reaching the pre-set potential (1600 mV), which type and amount of the initially formed PbSO4 phase will
 D. Pavlov et al. / Journal of Power Sources 137 (2004) 288–308 295

Fig. 9. Structure of the anodic layer formed after 1 h (a and b) and after 16 h (c and d) of cycling of a Pb/PbO2 /PbSO4 electrode in 2.86 M H2 SO4 solution.

depend on the solubility of PbSO4 in the H2 SO4 solution Fig. 9a that a considerable part of the PbSO4 crystals
as well as on the rates of PbSO4 nucleation and crystal have oxidized through a metasomatic process and the
growth. shape of the initial PbSO4 matrix has been preserved.
In our experiment the time for reaching 1600 mV was Let us call these PbO2 aggregates metasomatic ones.
about 3 ms. After 10 s of polarization at 1600 mV, electrode They are built of globular PbO2 particles sized 50–60 nm
cycling began between 1600 and 700 mV, thus allowing the (Fig. 9b).
secondary anodic structure to form. Fig. 9c and d presents the structure of the anodic
layer formed after 16 h of electrode cycling. Some of the
(a) 2.81 M H2 SO4 (1.17 s.g.): Fig. 9 presents SEM pictures metasomatic PbO2 aggregates have fully disintegrated
of the macro (Fig. 9a) and micro (Fig. 9b) structure of as a result of cycling and the obtained PbO2 particles
the anodic layer after 1 h of cycling. It can be seen from have formed shapeless agglomerates (Fig. 9d) or have
296 D. Pavlov et al. / Journal of Power Sources 137 (2004) 288–308

Fig. 10. Structure of the anodic layer formed after 1 h of cycling of a Pb/PbO2 /PbSO4 electrode in 1.58 M H2 SO4 solution. Long thin and flat rhombic
or rectangular metasomatic aggregates built up of PbO2 particles have formed.

precipitated on the surface of the PbO2 metasomatic over the other. They are thin, because they have formed
aggregates (Fig. 9c). within a thin reaction layer near the lead surface. In this
(b) 1.56 M H2 SO4 (1.095 s.g.): At this acid concentration, layer the flows of Pb2+ ions meet with the SO4 2− ions
the solubility of PbSO4 crystals is the highest (Fig. 3) coming from the solution [24]. A reaction of PbSO4 for-
and the anodic layer formed is composed mostly of mation proceeds, which results in PbSO4 crystal growth.
␤PbO2 (Fig. 2). Fig. 10 presents pictures of the anodic Depending on the intensity and the direction of the Pb2+
layer obtained after 1 h of electrode cycling. The pho- ion flow, PbSO4 crystals of different shapes are formed.
tographs feature long thin (Fig. 10c) and flat rhombic or When the electrode potential enters the PbO2 potential
rectangular metasomatic aggregates of PbO2 particles. region, these PbSO4 crystals are oxidized to PbO2 meta-
Fig. 10b presents a picture of a rhombic metasomatic somatic aggregates. During electrode cycling, destruc-
PbO2 aggregate. These aggregates are flat and grow one tion of the metasoamtic rhombic aggregates starts in
 D. Pavlov et al. / Journal of Power Sources 137 (2004) 288–308 297

their inner zones and advances towards the outer walls anisms depending on the precursor from which they
of the metasomatic aggregate. Fig. 10d shows SEM pic- originate.
tures of metasomatic PbO2 aggregates at higher mag- The process of disintegration of the endotaxial PbO2
nifications. The aggregates are built of globular PbO2 layers is clearly illustrated in the pictures of the anodic
particles sized from 40 to 50 nm. These are arranged in layer presented in Fig. 11d–f. The interconnection of
lines thus forming a wall or an edge. PbO2 particles in linear chains, not only on the surface
but also in the interior of the aggregate, is clearly visible
Elongated and rhombic PbSO4 crystals oxidize com- in these pictures (Fig. 11e and f). Disintegration of the
pletely to PbO2 metasomatic aggregates during electrode metasomatic aggregates proceeds through detachment of
cycling. This is confirmed by the XRD data. Fig. 10 illus- the linear chains from the aggregate. This implies that
trates the oriented growth of the new PbO2 phase, which is the binding energy of the PbO2 particles in the chain is
built up of PbO2 particles arranged in rows (Fig. 10c and sufficiently strong to keep the chain intact and prevent
d). The crystal lattice of PbSO4 influences strongly the ar- it from disintegration.
rangement of the PbO2 particles in the newly formed layers Fig. 12a and b presents SEM pictures of the anodic
of PbO2 phase (Fig. 10b and c). layer formed after 16 h of electrode cycling at polar-
When a crystal (new phase) grows onto the surface of ization up to 1600 mV. As a whole, the metasomatic
another crystal (substrate) and the crystal structure of the aggregates have been destroyed completely and a shape-
substrate affects or orients the crystal lattice of the new less microporous mass has formed. At this H2 SO4 con-
phase, the phenomenon is known as epitaxy. A similar phe- centration disintegration of the metasomatic aggregates
nomenon is observed when the PbSO4 crystal is oxidized proceeds faster than in more concentrated solutions.
to PbO2 metasomatic aggregate, but in this case, the new Fig. 12c and d shows the structure of the anodic layer
PbO2 phase grows towards the interior of the substrate (the formed after 16 h of electrode cycling whereby the po-
PbSO4 crystal). The latter crystal contributes to the process larization was stopped at 700 mV. Single PbSO4 crystals
by exerting an orienting effect on the arrangement of the are formed here and there between the PbO2 agglomer-
newly formed PbO2 particles into aggregates (Figs. 9b and ates. The obtained PbSO4 crystals are sized between 0.2
10). Let us call this phenomenon endotaxy, and the obtained and 1.0 ␮m and have cubic or prismatic shapes. During
oriented layers of PbO2 particles in the aggregate, endo- the subsequent anodic sweep, when the electrode poten-
taxial layers. During battery charge, endotaxy plays an im- tial enters the region of PbO2 stability, PbSO4 crystals
portant role in building the structure of the positive active are oxidized. Metasomatic processes depend on the con-
mass. centration of H2 SO4 and proceed only in PbSO4 crystals
greater than a certain critical size. When the size of the
3.7. Pb electrodes cycled in the passive low acid PbSO4 crystals is smaller than this critical value, they
concentration region form shapeless agglomerates.
(b) 0.18 M H2 SO4 solution (1.010 s.g.): Fig. 13 presents
(a) 0.5 M H2 SO4 (1.030 s.g.): Fig. 11 (1 h of electrode cy- pictures of the structure of the anodic layer and the
cling) presents pictures illustrating the stages of disin- morphology of the PbO2 particles after 1 h of elec-
tegration of the metasomatic aggregates obtained after trode cycling. There are no metasomatic PbO2 aggre-
oxidation of the initially formed PbSO4 crystals. The gates and the secondary structure consists of layers of
pictures in Fig. 11a and b feature a macrostructure com- particles as well as elongated prismatic aggregates with
prising long plate-like aggregates of PbO2 . It can be cross-section 1.5 ␮m × 2.0 ␮m (Fig. 13b and c). The
seen from Fig. 11c that the sizes of the PbO2 particles latter are composed of globular particles sized between
depend on the method of their formation. If formed as a 60 nm (spherical) and 160 nm (elongated) (Fig. 13c).
result of metasomatic oxidation of the PbSO4 crystals, The picture in Fig. 13b features some shapeless ag-
these particles are spherical in shape, sized between 50 gregates as well. PbO2 particles are formed there in
and 80 nm, and tightly adhering to each other thus form- rows and the band grows towards the bulk of the solu-
ing a film. A closer look at their arrangement evidences tion. Some of the PbO2 particles are arranged in layers
linear endotaxial chains. Fig. 11c (bottom right hand (Fig. 13b and c), thus forming a layered prismatic ag-
side of the picture) shows also that the newly formed gregate (Fig. 13c).
(secondary) PbO2 particles, over the shapeless microp- Fig. 13d–f presents pictures of another Pb/PbO2 /PbSO4
orous aggregates, are larger in size (between 160 and electrode cycled 1 h in 0.18 M H2 SO4 at a scan rate of
180 nm) and better shaped, i.e. the disintegration of the 100 mV/s. The PbO2 particles are flat, 200 nm in size
metasomatic aggregates on cycling is associated with and are either single or several of them interconnect to
changes in size, and probably also in structure and com- form a flat agglomerate.
position, of the PbO2 particles and their connection into After 16 h of cycling, the anodic layer contains zones
agglomerates and aggregates. Hence, the formation of of shapeless microporous agglomerates (Fig. 14a and
PbO2 particles proceeds through two different mech- b) and dendrites in other zones (Fig. 14c and d). The
298 D. Pavlov et al. / Journal of Power Sources 137 (2004) 288–308

Fig. 11. Structure of the anodic layer formed after 1 h of cycling of a Pb/PbO2 /PbSO4 electrode in 0.5 M H2 SO4 solution. (d–f) Illustrates the disintegration
of PbO2 metasomatic aggregates.

dendrites are 10–20 ␮m in length and 2.0–2.5 ␮m in 3.8. Influence of potential scan rate on the processes of
diameter. They are built of tightly interconnected PbO2 dendrite formation
particles with sizes between 100 and 150 nm (Fig. 14d).
(c) 0.05 M H2 SO4 solution. Fig. 15 presents pictures of the At the above low acid concentrations the solution is not
secondary PbO2 layer obtained after 1 h of cycling. The buffered and its pH at the electrode surface can change,
dendrites grow from certain sites of the primary PbO2 depending on the potential scan rate and on the ion dif-
layer (Fig. 15a and b). The pictures feature secondary fusion hindrances, and may approach the neutral region.
branches in some parts of the dendrites and individual Close to and within this pH range, hydrolysis of Pb2+ ions
PbO2 particles with crystal shape in other parts. Fig. 15c proceeds as well as formation of a number of complex
and d presents pictures of the anodic layer formed after ions of the type [Pb(OH)]+ , [Pb3 (OH)4 ]2+ , [Pb3 (OH)5 ]+ ,
1 h of electrode cycling, whereby the polarization was [Pb4 (OH)4 ]4+ and [Pb6 (OH)8 ]4+ [12].
stopped after reduction of PbO2 at 700 mV. Cubic and If the above hypothesis about the influence of complex
prismatic PbSO4 crystals are formed both over the pri- ions on the shape of the PbO2 aggregates is true, then
mary anodic layer and over the dendrites. The formation the potential scan rate should influence the shape of the
of dendrites is fully manifested after 16 h of electrode agglomerates. Potential sweeps were conducted within the
cycling. same potential range, 700–1600 mV at scan rates 2, 4, 10
 D. Pavlov et al. / Journal of Power Sources 137 (2004) 288–308 299

Fig. 12. Micro and macro structure of the anodic layer formed after 16 h of cycling of a Pb/PbO2 /PbSO4 electrode in 0.5 M H2 SO4 solution. Electrode
polarization was stopped at 1600 mV (a and b) and at 700 mV (c and d).

or 20 mV/s for 1, 2 or 16 h of electrode cycling in 0.05 M The latter are similar to the PbSO4 crystals presented in
H2 SO4 solution. Fig. 16a and b shows pictures of the an- Fig. 15c and d.
odic layer after 16 h of electrode cycling at 2 mV/s, whereby At potential scan rate 4 mV/s, the electrode stays 44 s in
the polarization was stopped at 1600 mV (Fig. 16a) and the PbSO4 potential region and 406 s in the PbO2 potential
at 700 mV (Fig. 16b), respectively. The electrode stayed region (Fig. 16c and d). After 16 h of cycling, small dendrites
87 s within the PbSO4 potential region and 813 s within are observed here and there in the anodic layer. This can
the PbO2 potential region. At this potential scan rate no be seen in the picture presented in Fig. 16c for electrode
dendrites are formed and many of the PbO2 particles have polarization up to 1600 mV. It is evident from the Fig. 16d
crystal shapes. The reduction of PbO2 proceeds in active that most of the dendrites have been reduced and PbSO4
centers where cubic PbSO4 crystals are formed (Fig. 16b). crystals have formed.
300 D. Pavlov et al. / Journal of Power Sources 137 (2004) 288–308

Fig. 13. Structure of the anodic layer formed after 1 h of cycling of a Pb/PbO2 /PbSO4 electrode in 0.18 M H2 SO4 solution. The anodic
layer comprises thin layers of particles and elongated prismatic aggregates (c), or flat particles, single or interconnected into flat agglomerates
(e and f).

Fig. 17 shows pictures of the anodic layer formed af- changes in the H2 SO4 concentration and in the potential
ter 16 h of electrode cycling at 10 mV/s (Fig. 17a and b) scan rate.
and at 20 mV/s (Fig. 17c and d). Many of the dendrites The above results indicate that the algorithms of
formed at both scan rates are wide, step-like geometric for- charge and discharge as well as the concentration of
mations, with frames on both sides of the dendrite (Fig. 17b the H2 SO4 solution are of utmost importance and de-
and c). termine the structure and electrochemical activity of
The pictures in Fig. 17d evidence that the dendrites are the Pb/PbO2 /PbSO4 electrode. Recently, pulse charge
built of small crystal-like particles arranged in rows. The algorithms have been employed for lead-acid batter-
primary anodic layer is relatively uniform and is com- ies for electric vehicle applications. The results of the
posed of PbO2 particles with crystal-like shapes (Fig. 17a present investigation evidence that the pulse charge mode,
and c). at certain H2 SO4 concentrations, has a strong influ-
On comparing Figs. 14, 15 and 17 is becomes evident that ence on the structure of the PbO2 particles, agglom-
the shape of the dendrites and their structure change with erates and aggregates, which in turn would affect the
 D. Pavlov et al. / Journal of Power Sources 137 (2004) 288–308 301

Fig. 14. Structure of the anodic layer formed after 16 h of cycling of a Pb/PbO2 /PbSO4 electrode in 0.18 M H2 SO4 solution.

electrochemical activity and cycle life of the lead-acid changes in a single parameter? We assumed that this param-
batteries. eter is the electrolyte composition.
The dissociation of sulfuric acid proceeds in two
steps:
4. Discussion of results
H2 SO4 + H2 O = H3 O+ + HSO4 − (3)
4.1. Dissociation of H2 SO4 and its effect on the aH3 O+ aHSO4 −
k1 = (3 )
electrochemical activity of PbO2 aH2 O aH2 SO4

The question arises whether the observed diversity in According to Young and Blatz [25], k1 = 103 . In its first
structure of the anodic layer could be a function of the step of dissociation, H2 SO4 is a strong acid.
302 D. Pavlov et al. / Journal of Power Sources 137 (2004) 288–308

Fig. 15. Structure of the anodic layer formed after 1 h of cycling of a Pb/PbO2 /PbSO4 electrode in 0.05 M H2 SO4 solution. Electrode polarization was
stopped at 1600 mV (a and b) and at 700 mV (c and d). The secondary anodic layer consists of dendrites unlike the primary layer which is built of
crystal-shaped PbO2 particles.

The second step of the dissociation is: ically determined by the equilibrium constants and depends
on the concentration of H2 SO4 in the system H2 SO4 /H2 O.
HSO4 − = H+ + SO4 2− (4) Fig. 18 shows the changes in concentration of the above
aH+ aSO4 2− components as a function of the H2 SO4 concentration, ac-
k2 = (4 ) cording to literature data [26–30]. The same figure gives
aHSO4 −
also the three acid concentration regions established by us
According to Covington et al. [26], k2 = 0.0102 (pk2 within which PbO2 has different electrochemical activity.
= 1.98). On comparing Figs. 1 and 2 with Fig. 18 we can draw
The ratio between the concentrations of H2 SO4 molecules the following conclusion. The curve reflecting the depen-
and HSO4 − and SO4 2− ions in the solution is thermodynam- dence of the concentration of HSO4 − ions versus H2 SO4
 D. Pavlov et al. / Journal of Power Sources 137 (2004) 288–308 303

Fig. 16. Anodic layer formed after 16 h of cycling of a Pb/PbO2 /PbSO4 electrode in 0.05 M H2 SO4 solution at potential scan rate 2 mV/s (a and b) and
4 mV/s (c and d). Electrode polarization was stopped at 1600 mV (a and c) and at 700 mV (b and d).

concentration is similar in profile to the curves giving the lead dioxide electrode has the highest electrochemical ac-
dependence of the electrochemical activity of PbO2 (Fig. 1) tivity.
and of the ␤PbO2 content in the anodic layer (Fig. 2) on the To be able to understand the influence of the ions of the
concentration of the H2 SO4 solution. This similarity gives solution on the electrochemical activity of the PbO2 phase
us grounds to assume that the latter two dependences are in- we should consider the structure of the PbO2 particles.
fluenced by the concentration of the HSO4 − ions in the so-
lution. The greatest amount of ␤PbO2 is found in the anodic 4.2. Composition and structure of PbO2 particles and
layer formed within the acid concentration region in which agglomerates
the concentration of HSO4 − ions is the highest. Hence, the
concentration of HSO4 − ions determines the formation of Lead oxides always react with water forming hydrated sur-
␤PbO2 . It is within this acid concentration region that the face layers. Lead dioxide particles comprise crystal (PbO2 )
304 D. Pavlov et al. / Journal of Power Sources 137 (2004) 288–308

Fig. 17. Structure of the anodic layer formed after 16 h of cycling of a Pb/PbO2 /PbSO4 electrode in 0.05 M H2 SO4 solution at scan rate 10 mV/s (a and
b) and 20 mV/s (c and d). Electrode polarization was stopped at 1600 mV.

and hydrated (gel) zones (PbO(OH)2 ·xH2 O) [17,31]. The them, which was also evidenced by XRD investigations in
crystal part consists of orthorhombic ␣PbO2 and/or tetrag- ref. [11]. Through shifting the equilibrium crystal ↔ gel
onal ␤PbO2 crystallites. The crystal and gel zones in the zones in one direction or the other, PbO2 particles of differ-
particles are in equilibrium. Another equilibrium exists also ent shapes are formed.
between the gel zones’ composition and the ions of the so-
lution [11]. PbO(OH)2 has amphoteric properties (H2 PbO3 ) (a) When the ions of the solution contribute to increas-
and can exchange both cations and anions with the solu- ing the volume of the crystal zones at the expense of
tion [11]. This makes the PbO2 particles and agglomerates the gel zones, the PbO2 particle acquires crystal shape
an open system. (For the sake of simplicity, we will refer (Figs. 7,8,16,17).
to this system as “PbO2 particles”.) Hence, the composition (b) When the ions of the solution facilitate the increase of
of the solution will affect the composition and structure of the gel zones in the PbO2 particle, the latter’s shape is
the gel and crystal zones as well as the proportion between drop-like or spherical (globular) (Figs. 4 and 10–13).
 D. Pavlov et al. / Journal of Power Sources 137 (2004) 288–308 305

Pb(OH)2 + HSO4 − + H+ → PbSO4 + 2H2 O

0.05 M

0.18 M

0.50 M
0.86 M
1.56 M
2.06 M
2.81 M
5.00 M
6.00 M

(6)

100 If the crystal zones predominate in the particles, the

HSO4-
volume of the gel zones is small and the number of
80 active centers is small, too, and so is the number of
PbO2 particles that can be reduced. Hence, the lead
Active H2SO4

dioxide has low electrochemical activity, i.e. low capa-

region
concentration

60
C /wt. %

Passive region
Passive region

city.
If the gel zones predominate greatly in the particle, its
40 SO42- electrochemical activity is somewhat reduced because of
the impeded electron transport. Only a definite proportion
20 H2SO4 between the crystal and gel zones in the PbO2 particles
make them electrochemically active [31]. The greater the
0 number of particles with optimum ratio between gel and
0,001 0,01 0,1 1 10 crystal zones, the higher the capacity of the PbO2 /PbSO4
MH2SO4 / mol.l-1 electrode. Based on the gel-crystal model for the struc-
Fig. 18. Concentration of SO4 2− and HSO4 − ions resulting from the ture of the PbO2 particles, the influence of HSO4 − ions on
dissociation of H2 SO4 vs. H2 SO4 concentration [26–30]. the electrochemical activity of these particles can be ex-
plained as follows. At H2 SO4 concentrations from 5.0 to
0.5 M, the equilibrium between the HSO4 − ions in the gel
The reactions of PbO2 reduction proceed in active centers
zones and in the solution maintains optimum proportion be-
located in the hydrated (gel) zones [32]. Hence, the electro-
tween the gel and crystal zones in the particles. The latter
chemical activity of the lead dioxide will depend on the ratio
are drop-like in shape, i.e. they contain substantial volume
crystal/gel zones and on the concentration of active centers
of gel zones. The concentration of active centers in these
in the gel zones.
particles is high and hence the electrochemical reaction of
PbO2 reduction proceeds at a high rate. The high concen-
4.3. Processes of PbO2 reduction and effect of sulfuric tration of HSO4 − ions in the solution keeps up the opti-
acid ions on these processes mum ratio between the gel and crystal zones in a maximum
number of PbO2 particles that are in contact with the so-
The PbO2 particles interconnect into agglomerates, ag- lution. Hence, the capacity of the PbO2 /PbSO4 electrode is
gregates and skeleton. Their crystal zones are also intercon- high.
nected. The crystal zones are degenerated semi-conductors In the passive region with the lowest H2 SO4 concentra-
[33] with electron conductivity, i.e. they conduct the current tion, the content of SO4 2− ions in the solution increases
from the current collector to the site of the electrochemical at the expense of the reduced concentration of HSO4 −
reaction (active center) and in the opposite direction. For the ions. This leads to the formation of ␣PbO2 phase in the
electrochemical reaction of PbO2 reduction to proceed in a particles and its content increases on diluting the solu-
given active center, it is necessary that both electrons and tion, whereas the content of the ␤PbO2 phase diminishes
protons reach this center. This may happen in the gel zones (Fig. 2). On sweeping the potential at a high rate, dendrites
of the particles. If charges of one type only (electrons or H+ of crystal-like particles are formed (Figs. 15 and 17). At low
ions) reach the active center, the latter will be charged elec- potential scan rate, crystal shaped PbO2 particles are formed
trically and so will the whole gel zone. Consequently, the (Fig. 16a and b). These particles contain small volume of
reaction will stop. For the reaction to proceed, the charges gel zones and hence their electrochemical activity is low
of the gel zone should be neutralized, which is achieved by (Fig. 1).
attracting electrical particles with the opposite charge to en- In the passive region of high H2 SO4 concentrations, the
ter the gel zone. concentration of H2 SO4 molecules in the solution increases,
The gel zones are both ion conductive and electron con- while that of the HSO4 − ions decreases (Fig. 18). PbO2 par-
ductive, and thus provide the transfer of H+ ions from the ticles with crystal-like shape (Figs. 7 and 8) of the ␣PbO2
solution to the active centers and of electrons from the crys- modification (Fig. 2) are formed. The ␤PbO2 content de-
tal zones to the active centers and in the opposite direction. creases.
The following reaction of PbO2 reduction proceeds in the The two passive regions have the following features in
active centers: common: crystal-shaped PbO2 particles, reduced volume of
PbO(OH)2 + 2H+ + 2e− → Pb(OH)2 + H2 O (5) the gel zones and hence lower concentration of active cen-
ters in these zones, increased content of the ␣PbO2 phase,
The water formed as a result of this reaction dilutes the smaller number of PbO2 particles that can be reduced and
gel zones. Pb(OH)2 gets in contact with the sulfuric acid consequently, lower capacity of the PbO2 /PbSO4 electrode
and a reaction of sulfation proceeds: (Fig. 1).
306 D. Pavlov et al. / Journal of Power Sources 137 (2004) 288–308

4.4. Influence of ions in the H2 SO4 solution on the Further reactions proceed in two directions, the first one
processes of oxidation of the PbSO4 crystals in the active being the formation of ␣PbO2 :
region of H2 SO4 concentrations
PbO(OH)(HSO4 ) → ␣PbO2 + H2 SO4 (10 )
If we compare the data for the solubility of PbSO4 crystals and the second one is the interaction with water:
as a function of the H2 SO4 concentration (Fig. 3) with those
for the concentration of HSO4 − ions in the solution (Fig. 18), PbO(OH)(HSO4 ) + H2 O = PbO(OH)2 + H2 SO4 (10 )
we can see that PbSO4 has the highest solubility within the The latter two reactions result in the formation of parti-
region of high concentration of HSO4 − ions in the solution. cles with gel and crystal zones. The gel zones contain some
Figs. 9 and 10 show that, in this concentration region, PbSO4 PbO(OH)(HSO4 ) molecules which probably reduce consid-
crystals are oxidized through metasomatic processes. The erably their electron and ion conductivity as well as the num-
oxidation of PbSO4 must result in the formation of HSO4 − ber of active centers in them. The electrochemical activity
ions. This may happen if the following reaction proceeds: of the PbO2 /PbSO4 electrode declines substantially.
The picture in Fig. 7a evidences that ␣PbO2 crystal-shaped
PbSO4 + 3H2 O → PbO(OH)2 + HSO4 − + 2e− + 3H+ particles arrange in the volume of the PbSO4 crystal being
(7) oxidized in such a way that the shape of the obtained ag-
glomerate is rough and differs from the shape of the initial
HSO4 − and H+ ions get into the solution and drop-like PbSO4 crystal. This type of PbO2 agglomerates differ from
PbO(OH)2 particles are formed. This reaction may proceed those presented in Figs. 9–12, which indicates that the oxi-
on those parts of the PbSO4 surface where electrons can dation of the PbSO4 crystal to PbO2 agglomerate proceeds
pass from the PbSO4 crystal to the lead dioxide phase and via a different mechanism.
through it to the current collector.
In the drop-like particles, a reaction of dehydration and 4.6. Oxidation of PbSO4 crystals in the passive region of
formation of ␤PbO2 crystal zones proceeds. The following low H2 SO4 concentrations
equilibrium is established:
PbO(OH)2 ⇔ ␤PbO2 + H2 O (8) Figs. 13–17 show that, in this acid concentration region,
there is no similarity in shape of the PbSO4 crystals and
Fig. 9 shows that, at 2.81 M H2 SO4 concentration, the PbO2 aggregates. This implies that the processes of oxida-
PbSO4 crystals are covered, completely or partially, with tion of PbSO4 to PbO2 involve a step during which the Pb2+
a lead dioxide layer that grows inside the volume of the ions pass through the solution prior to being oxidized to
PbSO4 crystals forming oriented endotaxial layers of PbO2 Pb4+ ions.
particles. The microstructure of these layers can be seen in In analogy to the mechanism of the processes of elec-
Figs. 9b and 10c and d. The mechanism of disintegration of trochemical reduction of the metal ions and formation of
these layers into individual PbO2 particles or rows of parti- the metal crystal lattice during electroplating, the following
cles can be observed in Figs. 10d and 11e and f. During the stages of the process of oxidation of PbSO4 to PbO2 can be
subsequent electrode discharges, PbSO4 crystals are formed assumed for this particular case:
at different sites and of different shape and size than the pri- (i) Dissolution of the PbSO4 crystal through the reaction
mary PbSO4 crystals. Thus, the primary PbO2 aggregates
disintegrate into a porous mass of shapeless agglomerates PbSO4 = Pb2+ + SO4 2−
and aggregates. The electrode is electrochemically active
and its life depends on the strength of the bonds between (ii) Diffusion of the Pb2+ and SO4 2− ions from the PbSO4
the individual agglomerates and aggregates. Such processes surface to the bulk of the solution. SO4 2− ions are stable
take place in the positive active mass, too, whereby its ini- in this acid concentration region (Fig. 18).
tial structure formed during plate formation, changes into a (iii) Depending on the pH of the solution, Pb2+ ions may
new structure during cycling [35]. form a number of complexes with OH-ions [12,34].
(iv) Adsorption of the Pb2+ complexes or Pb2+ ions on the
4.5. Oxidation of PbSO4 crystals in the passive region of surface of the lead dioxide particles and agglomerates
and their diffusion until they reach an active center on
high H2 SO4 concentrations
the surface or into the interior of the gel zones, where
the two-valent Pb2+ ions or complexes will be oxidized
As evident from Figs. 7 and 8, the PbO2 particles formed
to four-valent ones.
in this acid concentration region are crystal shaped and of
(v) Hydration of the four-valent Pb4+ ions or rearrange-
the ␣PbO2 species; some unoxidized PbSO4 remains in the
ment of the hydrated complexes and their incorpora-
anodic layer as well (Fig. 2). In this case, the oxidation of the
tion into the lead dioxide particles, or nucleation and
PbSO4 crystals involves less water and follows the reaction:
growth of new lead dioxide particles. At this stage the
PbSO4 + 2H2 O = PbO(OH)(HSO4 ) + 2e− + 2H+ (9) lead dioxide particle grows or a new particle is formed.
 D. Pavlov et al. / Journal of Power Sources 137 (2004) 288–308 307

(vi) Interconnection of the lead dioxide particles into ag- 100

glomerates or aggregates. The hydrated layers of the
lead dioxide particles interconnect and an interaction 80
Shedded deposit / %

is established between the crystal and gel zones within

60
an agglomerate. If the interaction between the particles
building the agglomerate is weak, they shed off. If the 40
interparticle interaction is strong, whereby an equilib-
rium is established between all gel and crystal zones 20
throughout the agglomerate, they build a strong skele-
ton. 0
0,01 0,1 1 10
The above processes are much more complicated than MH2SO4 / mol.l -1

the process of reduction of the metal ions, as they involve Fig. 19. Shedding of the anodic layer as a function of H2 SO4 concentration
building of the structure of a compound, and probably the [6].
above elementary processes are not the only ones. All these
processes will be influenced both by the H2 SO4 concentra- should not fall down below 1.5 M H2 SO4 . Hence, there is a
tion and by the potential scan rate. As the H2 SO4 solution lower limit of the decrease of the acid concentration during
is highly diluted and not buffered, the changes in potential discharge. The upper acid concentration limit is 5 M H2 SO4 ,
may lead to the formation of a diffusion layer at the PbO2 above which the region of passivation of the PbO2 /PbSO4
surface with a different pH than that of the bulk solution, electrode starts. Thus, the working interval within which the
which will have a considerable effect on the formation of concentration of the H2 SO4 solution may change on cycling
complexes. At 0.18 M H2 SO4 concentration and potential is from 5.0 M H2 SO4 (1.28 s.g.) to 1.5 M H2 SO4 (1.10 s.g.),
scan rate of 100 mV/s, flat lead dioxide particles are formed i.e. 3.5 M H2 SO4 per 1 l of H2 SO4 solution with s.g. 1.28
sized about 100 nm (Fig. 13e and f) or cylindrical agglom- takes part in the reactions on both battery plates.
erates (Fig. 13b and c) comprising layers of PbO2 particles It is well known that Sb, Sn and Bi ions have a benefi-
with dimensions about 80–100 nm. When the H2 SO4 con- cial effect on the cycle life of lead-acid batteries [36]. The
centration is 0.05 M and the potential scan rate is >10 mV/s, proposed model for the processes in the PbO2 particles can
long lead dioxide dendrites are formed (Figs. 15 and 17). explain the mechanism of influence of the above ions. This
The dendrites illustrated in Fig. 17a and b (at 10 mV/s) and model could help in finding new more efficient additives to
Fig. 17c and d (at 20 mV/s) feature step-like crystal forms the electrolyte, which would improve the performance of the
built up of ordered individual particles. It can be assumed batteries.
that the structure of the lead complexes does exert a strong The capacity of the positive plate may decline as a result
influence on the agglomerates’ shape of the newly formed of local passivation or disintegration of the PAM structure in
phase. Generally, lead(II) complexes contain various Pb2+ the plate interior when the H2 SO4 concentration enters one
and OH− ions (for example [Pb4 (OH)4 ]4+ , [Pb6 (OH)8 ]4+ , of the two passive concentration regions. In order to guar-
etc.), whose structure is transferred to the new phase during antee the reversibility of the PAM structure during charge
the oxidation of Pb2+ to Pb4+ . Thus, the newly formed par- and discharge, the H2 SO4 concentration in the PAM pores
ticles may have a shape influenced by the structure of the should be maintained within the above mentioned limits.
initial Pb2+ complexes. An interesting fact is that PbO2 par- This can be achieved through an appropriate ratio between
ticles of nano-sizes arrange in crystal-shaped agglomerates the quantities of the four active materials (Pb, PbO2 , H2 SO4
(Fig. 17). and H2 O) in the lead-acid cell and the densities of PAM and
NAM.
4.7. Determining the maximum amount of H2 SO4 that can
take part in the discharge reactions in the lead-acid battery
without causing disintegration or passivation of PAM References

In a previous investigation of ours we have established [1] Z. Takehara, K. Kanamura, Electrochim. Acta 29 (1984) 1643.
that within a certain H2 SO4 concentration region part of the [2] Z. Takehara, K. Kanamura, J. Electrochem. Soc. 134 (1987) 13.
[3] Z. Takehara, K. Kanamura, J. Electrochem. Soc. 134 (1987) 1604.
anodic layer sheds off [6]. Fig. 19 presents this dependence [4] P. Ekdunge, D. Simonsson, J. Electrochem. Soc. 132 (1985) 2529.
of the amount of shed off anodic layer after 16 h of elec- [5] A. Czerwinski, M. Zelazowska, M. Grden, K. Kuc, J.D. Milewski, A.
trode cycling in H2 SO4 solutions of various concentrations. Nowacki, G. Wojcik, M. Kopczyk, J. Power Sources 85 (2000) 49.
It can be seen that the most intense shedding of particles [6] B. Monahov, D. Pavlov, A. Kirchev, S. Vasilev, J. Power Sources
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[7] G.W. Vinal, D.N. Craig, J. Res. Bur. Stand. 22 (1939) 55.
from 1.5 M H2 SO4 (1.095 s.g.) to 0.5 M H2 SO4 (1.030 s.g.). [8] V. Danel, V. Plichon, Electrochim. Acta 27 (1982) 771.
In order to guarantee long cycle life of the lead-acid cell, [9] I.G. Kiseleva, B.N. Kabanov, Dokl. Akad. Nauk SSSR 122 (1956)
not limited by shedding of PAM, the H2 SO4 concentration 1042.
308 D. Pavlov et al. / Journal of Power Sources 137 (2004) 288–308

[10] G.A. Kokarev, V.A. Kolesnikov, M.Ya. Fioshiu, Elektrokhimiya [23] D. Pavlov, Z. Dinev, J. Electrochem. Soc. 127 (1980) 855.
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