854 J. Electrochem. Soc.

: E L E C T R O C H E M I C A L S C I E N C E A N D T E C H N O L O G Y July 1974

Manuscript submitted Nov. 27, 1973; revised m a n u -
script received Feb. 26, 1974.
A n y discussion of this paper will appear in a Discus-
sion Section to be published in the J u n e 1975 JOUaNAL.
All discussions for the J u n e 1975 Discussion Section
should be submitted by Feb. 1, 1975.
REFERENCES
1. G. V. Lago, J. P. Karnes, J. B. Jennings, and R. L.
Smith, F i n a l Report, Contract DA-36-039-SC-
74994 (PB 143899) (March 1959).
2. M. Arcand, F i n a l Report, Contract DA-36-039-SC-
72363 (PB 135749) ( J u l y 1957).
3. F. Solomon, Proc. Ann. Battery Res. Develop. ConS.,
12, 94 (1958).
4. I. M. Kolthoff and J. F. Coetzee, J. Am. Chem. Soc.,
79, 1852 (1957).
5. S. G. Biallozor, Electrochim. Acta, 17, 1243 (1972).
6. J. K. Senne and B. Kratochvil, Anal. Chem., 44, 585
(1972).
7. J. F. Coetzee, G. P. C u n n i n g h a m , D. K. McGuire,
and G. R. P a d m a n a b h a n , ibid., 34, 1139 (I962).

Formation Processesof the Lead-Acid Battery Negative Plates

D. Pavlov, V. Iliev, G. Papazov, and E. Bashtavelova
Bulgaria~z Academy ol Sciences, Institute of Physical Chemistry,
Division ol Electrochemical Power Sources, Sofia 13, Bulgaria

ABSTRACT
The advance of the processes within the bulk of the negative plate upon
formation i n sulfuric acid was studied b y electron-microprobe and x - r a y
diffraction experiments a n d by microscopic observations. It was found that
besides the electrochemical reaction of the formation of sponge lead there
were also chemical reactions of the formation of lead sulfate which r e m a i n
included i n the lead n e t w o r k of crystals. The electrochemical reduction of lead
sulfate takes place after the consumption of lead oxide and tribasic lead sul-
fate present i n the paste. The e l e m e n t a r y chemical and electrochemical re-
actions as well as their m u t u a l relationships are d e t e r m i n e d as the basis of
these measurements.
The change in total porosity and pore size distribution d u r i n g formation
of the lead-acid b a t t e r y negative plate was studied. Upon formation, both the
pore radii and the porosity of the active mass increase. The electrocrystal-
lization processes of lead during formation are also discussed. Upon reduction
of 3PbO 9 PbSO4 9 H20 and PbO a lead crystal n e t w o r k is formed i n the first
stage. During the second stage, lead, obtained b y reduction of lead sulfate, is
deposited on the network.

The technology of lead-acid b a t t e r y plates includes
the following stages. By the m i x i n g of a partially oxi-
dized lead powder with a sulfuric acid solution a paste
is obtained which consists of lead hydrate, lead m o n o x -
ide, and basic lead sulfates. Besides these compounds
the negative plate paste also contains b a r i u m sulfate
and an expander. After pasting on a grid and curing,
the paste is subjected to formation. D u r i n g formation,
the lead monoxide and the basic sulfates are trans-
formed by electrochemical reactions into active m a t e -
rial, i.e., lead at the negative plate and lead dioxide at
the positive one.
The influence of b a r i u m sulfate, of the expander, a n d
of the conditions of formation on the properties of the
negative plate have been studied previously (1-11).
The microstructure of the lead crystals obtained upon
formation, as well as the way in which these crystals
grow, has already been investigated (12-15). The
chemical and electrochemical reactions which take
place upon formation have been presented by Pavlov
(15).
The aim of the present paper is to establish the ele-
mentary chemical, electrochemical, and crystallization
processes which occur during the formation process
and to elucidate their mutual relationships.
Experimental
Traction b a t t e r y plates with dimensions of 285 X 180
X 4 m m were formed. They were produced with a
paste containing 4.5% sulfuric acid, b a r i u m sulfate, and
expander. The formation was effected i n two cells, each
Key words: l e a d - a c i d battery, lead-acid b a t t e r y technology, l e a d
electrode, f o r m a t i o n of t h e lead electrode, reactions in porous
masses.
constituting two positive a n d one negative plate. A
sulfuric acid solution of density 1.05 was used in a
volume of 3000 cm s. For every gram of paste there was
1.89 cm 3 of sulfuric acid solution. I m m e d i a t e l y after
pouring the solution in the cells, a c u r r e n t density of
10.00 m A / c m 2 was applied. The following parameters
were checked d u r i n g formation at 2 h r intervals: (i)
density and t e m p e r a t u r e of the sulfuric acid solution;
(ii) distribution of lead over the cross section of the
plate; (iii) distribution of lead sulfate over the cross
section of the plate; (iv) phase composition at the sur-
faces a n d in the b u l k of the plate; (v) total porosity
and pore size distribution at the surfaces a n d i n the
b u l k of the plate.
Samples were t a k e n of the negative plates for de-
t e r m i n a t i o n s (ii)- (v). I n order to eliminate differences
along the height and width of the plates, m a t e r i a l was
taken from three different locations of the plates. The
samples were collected in the following m a n n e r . At
2 hr intervals the formation process was stopped. The
negative plates were removed from the cells and
washed with water. Three portions were removed from
each plate, each containing four grid rectangles. The
plates were then r e t u r n e d into the cells, the c u r r e n t
was corrected, and the formation process was resumed.
The six samples were a b u n d a n t l y washed with w a t e r
and dried in a nitrogen atmosphere. The samples t a k e n
from one of the negative plates were used for observ-
ing the distribution of lead along the cross section of
the plate and for d e t e r m i n i n g the distribution of lead
sulfate across the cross section of the plate. The sam-
ples from the second negative plate were used for
phase composition and porosity studies.

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 Vol. 121, No. 7 LEAD-ACID BATTERY NEGATIVE PLATES 855

Determination of the Elementary Chemical and

Electrochemical Reactions
Change in the sulfuric acid concentration in the bulk
o] the electrolyte during ]ormation.--The f o r m a t i o n of
the b a t t e r y plates takes place in a sulfuric acid solu-
tion. Lead m o n o x i d e and the basic sulfates are unstable
in sulfuric acid. This is w h y chemical sulfatization re-
actions of the lead m o n o x i d e and of the basic sulfates
take place parallel w i t h the electrochemical reactions.
The participation of t h e sulfuric acid in the chemical
reactions leads to a change in its concentration w i t h i n
the b u l k of the electrolyte. The density changes of sul-
furic acid w i t h i n the bulk of the electrolyte during
formation are r e p r e s e n t e d in Fig. 1. Two stages can be
observed on this curve. During the first stage sulfuric
acid penetrates into the plates and reacts w i t h the
pastes, and hence its concentration in the b u l k of the
electrolyte decreases. D u r i n g the second stage the sul-
fate products obtained during the first stage are
formed. Sulfuric acid is e v o l v e d as a result of these
reactions. It leaves the plates thus increasing the sul-
furic acid concentration in t h e b u l k of the electrolyte.
Advance of the reactions of formation of lead across
the cross section of the plate.--The samples w e r e en-
closed in a l u m i n u m molds and soaked u n d e r v a c u u m
w i t h polyester resin. A f t e r h a r d e n i n g of the resin, the
samples w e r e m a c h i n e d until the cross section of the
plate appeared clearly. A f t e r d r y polishing the cross
section was o b s e r v e d u n d e r a microscope and photo-
g r a p h e d on color and b l a c k - a n d - w h i t e films. Such
micrographs are illustrated in Fig. 2. It is easily seen
that t h e formation of lead begins first at those portions
of the m e m b e r grid that are closest to the solution.
Lead forms zones w h i c h advance at the surface of the
plates (Fig. 2b). In those portions of t h e plate surface
not already occupied by the lead zones the paste reacts
w i t h sulfuric acid and w h i t e lead sulfate zones origi-
nate (Fig. 2b). A f t e r the lead zones h a v e covered the
surface of the plate t h e y advance into the paste (Fig.
2c-e). F r o m the photographs it is seen that a thin l a y e r
of w h i t e crystals occurs at the b o u n d a r y b e t w e e n the
lead zone and the u n f o r m e d paste. B e t w e e n the sixth
and the eighth h o u r of formation the entire cross sec-
tion of the plate is occupied by the lead zone. The for-
m a t i o n process ends at the f o u r t e e n t h hour, w h e n the
lead mass has b e c o m e d a r k - g r a y in color.
Determination of the distribution of lead sulfate
across the cross section of the plate.--The samples
selected for these studies w e r e placed in cylindrical
a l u m i n u m molds w h i c h w e r e filled w i t h e p o x y resin.
A f t e r h a r d e n i n g of the resin the m o l d was cut so that
the sample was divided into two identical halves. A f t e r
Fig. 2. Micrograph of the crass section of the negative plate
during formation, a, Prior to formation; b-e, plates during forma-
tion (the dark patches are the lead zone); f, fully formed plate.
~,o6
d r y polishing, a conductive 100-150A thick carbon l a y e r
1,05, was deposited on the cross section. The d e t e r m i n a t i o n
of the sulfur distribution across the cross section of the
m plate was carried out w i t h a Hitachi X M A - 5 electron
1.0,
IO~ T M
microprobe. The electron b e a m was scanned r e p e a t e d l y
across a 240 • 240~ area and the intensity of the sulfur
"0
line was recorded. In this w a y the a v e r a g e s u l f u r con-
1,03 tent o v e r the scanned areas was determined. The elec-
t r o n beam was t h e n scanned on the following point.
These m e a s u r e m e n t s m a d e it possible to establish t h e
1,02 distribution of lead sulfate along t h e cross section p e r -
pendicular to the plate surface.
F i g u r e 3 represents the results of the m e a s u r e d rela-
Wl ! I | I I I
tive amounts of lead sulfate (free and bonded in the
0 2 4 6 8 10 12 14 basic sulfate). The thickness of the plate is plotted in
r e l a t i v e units on the abscissas axis. F r o m the figure it
time in hours
can be seen that lead sulfate is first f o r m e d at the sur-
Fig. 1. Change in the electrolyte density within the bulk of the face of the plate. Then it advances slowly into the i n n e r
electrolyte during formation. parts of the paste. At the eighth h o u r of f o r m a t i o n lead

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 856 J. Electrochem. S o c . : E L E C T R O C H E M I C A L S C I E N C E A N D TECHNOLOGY J u l y 1974

Oh / Phase composition studies of the paste during forma-

tion.--The samples were divided across the cross sec-
tion into three portions: two at the surfaces a n d one in
the bulk. The surface portions were joined together.
, , ' t After grinding, the samples were x - r a y e d with a TuR
M-61 diffractometer with filtered copper radiation.
40k 2h /~ The q u a n t i t a t i v e x - r a y phase analysis is based on the
equation
xi x!
Ii--K~-'K
piZxjm~ mm
where It is the i n t e n s i t y of the analytical x - r a y reflec-
o I I t tion of the phase we wish to determine, K is a n ap-
- 60 4h paratus constant, xi the weight percentage of the ith
phase in the mixture, pi is the density of the ith phase,
mj is the specific absorption coefficient of x - r a y s b y the
:,,o j t h phase, and m is the average absorption coefficient
of the sample.
i n a t h r e e - c o m p o n e n t system, w h e n the i n t e n s i t y of
a20 the analytical reflection of a given phase is referred to
-i the sum of the intensities of the analytical reflections of
the three phases, the average absorption coefficient, m,
o I I I and the apparatus constant, K, are eliminated from the
| 6(] 6h equation. For the first phase the relative i n t e n s i t y is
given by the expression

4O II Xl

P1 ( ) ~/~1-"~- - -X2"~
- - xs

i~
I1"~I2~'I3
pl pg p8
/ For a given sample the term included in brackets re-
I I I mains constant in the expressions referring to the three
phases.
"
o 40 ~ e.,,.-, e Lx,. The aim of the present investigation is to establish
the e l e m e n t a r y reactions which take place d u r i n g for-
m a t i o n of the plate. It is therefore sufficient to find
w
the changes in the amounts of the i n d i v i d u a l phases
= 20 present in the paste d u r i n g formation, a n d it is not
ut
necessary to d e t e r m i n e their absolute contents. I n this
case the x - r a y diffraction method m a y be used only for
0' I I I
d e t e r m i n i n g the changes in the relative intensities of
the reflections. The error introduced in this deter-
D m i n a t i o n depends on the densities of the components.
The analysis of the x - r a y diffraction p a t t e r n s i n d i -
cates that the cured paste of the negative plate con-
sists of considerable amounts of tet. PbO and tribasic
lead sulfate and m i n o r amounts of lead. The following
x - r a y reflections were used in the study of the change
o I I I in the a m o u n t s of each phase: d = 3.26A for 3PbO 9
20 12h PbSO4. 9 H20, d = 3.00A for PbSO4. The reflection with
d -- 3.12A corresponds to tet. PbO (the strongest re-
flection in the p a t t e r n ) and overlaps with the 3.13A
reflection of 3PbO 9 PbSO4 9 H20 (I = 35). The 2.86A
%oo o2s o,5o 0.75 1.oo reflection corresponds to lead (I = 90 of the p a t t e r n )
relative thickness of the plate and overlaps with the 2.84A reflection (I = 10) of
3PbO 9 PbSO4 9 H20.
Fig. 3. Change in the distribution of the total amount of lead sul- Figure 4 illustrates the change i n the relative i n -
fate along the cross section of the plate during formation. tensities of the reflections of the i n d i v i d u a l phases at
the surface and i n the b u l k of the plate d u r i n g forma-
tion. It should be noted that the n u m e r i c a l values of
sulfate is almost u n i f o r m l y distributed across the e n -
the relative intensities do not reflect the relative
tire cross section of the plate. The reduction of lead
amounts of the phases in the mixture. It is seen that
sulfate takes place after the eighth h o u r along the en-
during formation, lead oxide a n d tribasic sulfate react
tire cross section of the plate. However, this process is
with sulfuric acid thus leaving lead sulfate in the paste
most rapid at the surface of the plate (Fig. 3).
adjacent to the surfaces. The formation of lead i n the
The results of these m e a s u r e m e n t s indicate that the
first 4 hr occurs only at the surface parts of the plate
processes of sulfatization of lead oxide and of tribasic
b y electrochemical reduction of lead oxide and tribasic
lead sulfate take place from the surface toward the
sulfate. After the eighth hour, the reduction of the lead
interior of the plate. F r o m Fig. 2 it is seen that the
sulfate formed d u r i n g formation begins. This reduction
advance of the lead zone follows a similar path. The
begins first at the surface, and at the f o u r t e e n t h hour
end of the sulfatization of the paste occurs at about the
same time w h e n the lead zone occupies the entire plate. the negative plate is e n t i r e l y formed.
This indicates that a relationship exists b e t w e e n the Elementary chemical and electrochemical reactions
processes of formation of lead and lead sulfate. After and their mutual relationships.--From the results of
that, the reduction of lead sulfate occurs in the whole Fig. 2-4 a model can b e suggested for the e l e m e n t a r y
lead zone b u t most r a p i d l y i n the surface portions of chemical and electrochemical reactions and for the
the plate. elucidation of their m u t u a l relationships. This model

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 VoL I21, No. 7 LEAD-ACID BATTERY NEGATIVE PLATES 857

i n the electrochemical reaction [1'] i n which lead is

formed, and in the chemical reactions [3] and [4],
which are conducive to tribasic lead sulfate and lead
sulfate. The h y d r o x y l ions participate not only i n r e -
action [3] b u t also i n the n e u t r a l i z a t i o n reaction [2].
On the one h a n d reaction [2] influences the dissolution
rate of PbO (reaction [ A ] ) , and on the other, controls
the pH of the pore solution at the considered place in
the paste. It should be stressed that the n a t u r e of the
o lead ions which are i n e q u i l i b r i u m with lead oxide, tri-
o
d =3,26 A basic sulfate, a n d lead sulfate, and which participate i n
the electrochemical reaction [1'], depends on the pH
of the solution. At low pH the lead ions are free P b 2+
ions; at pH > 6 they are b o n d e d in complexes such as
P b ( O H ) +, Pb(OH)2, P b ( O H ) ~ - , a n d H P b O 2 - . For
simplicity let us assume that only P b 2+ ions originate
oI ~ ' ' ~ ~ i n the pores. This m e a n s that the rate of the decom-
J d = 3,00 A position reactions of the complexes are infinitely large.
If the flow of sulfuric acid a r r i v i n g from the b u l k of
201- o......o.-.--o o~ the electrolyte toward a given location of the plate
which contains lead oxide is smaller t h a n the dissolu-
tion rate of lead oxide (reaction [ A ] ) , the pH of the
pore solution will be close to neutral. As a result re-
~ ioo action [3] occurs in the paste, and tribasic lead sulfate
crystals will grow. If the sulfuric acid flow from the
'--' 80 b u l k of the electrolyte to the given location is larger
t h a n the dissolution rate of lead oxide (reaction [A]),
the pH of the solution will be low, reaction [4] will
6o take place, and lead sulfate will form. I n the pres-
ence of a n electrode surface (lead mass) close to t~e
location, the electrochemical reaction [1'] takes place.
4o This reaction is the electrochemical reduction of lead
oxide to lead. The e q u i l i b r i u m potential of this reaction
is given b y Eq. [ l ' a ]
PbO+2e+2H + =Pb+H~O
o I I | | | I
o 2 4 6 8 10 12 14 E = 0.248 -- 0.059 p H [l'a]
time tn hours
Figure 5b gives the diagram of the e l e m e n t a r y chem-
Fig. 4. Change in the phase composition of the negative plate ical and electrochemical reactions which occur w h e n
during formation, d ~ 3.12A, tet. PbO + 3PhO 9 PbSO4 9 H20. 3 P b O . PbSO4. H~O is the starting material. As a re-
d - - 3.26A, 3PbO 9 PbSO4 9 H20, d ~- 3.00A, PbSO4. d - - 2.86A, sult of the dissolution of tribasic lead sulfate (reac-
Pb + 3PbO - PbSO4 9 H20. O , At the surface of the plate; 4,, tion [B]) the pore solution contains P b 2+, O H - , and
in the bulk of the plate. SOi~- ions. The P b 2+ ions m a y participate both i n the
electrochemical reaction 1" a n d in the chemical re-
action [4]. W h e t h e r reaction [4] will occur or not de-
should include the e l e m e n t a r y reactions which occur pends on the accession of sulfuric acid from the b u l k
from the two starting compounds of the paste, lead of the electrolyte. If this flow is larger t h a n the dis-
oxide and tribasic lead sulfate. solution rate of 3 P b O . PbSO~. H~O the pH of the
Figure 5a diagrammatically shows the reactions pore solution will be low. Reaction [4] will t h e n take
w h e n lead oxide is the s t a r t i n g compound. Divalent place, yielding lead sulfate. The lead ions which are
lead ions and O H - ions are formed u p o n dissolution of generated upon dissolution of 3PbO 9 PbSO4 9 H20 p a r -
the oxide (reaction [A] ). The lead ions m a y participate ticipate i n the electrochemical reaction [1"]. The e q u i -
l i b r i u m potential of the P b / 3 P b O " PbSO4" H~O elec-
trode is g i v e n b y the equation
I
I
H§ III
I I
I a 4-
Q H* * OH& HzO QmP~*+ 2 me-- mPb I
i
i
I I J. IH2S04 Q6H** 6OH-= 6H20 (~) nPb~+2ne~ Pb
I
@ PbO+H20 ~--20H-§ Pb
paste
t , t , q

I (~)3PbOPbSO4H20+2H20--"- 6OH-+4Pb2 + SO~- H~S04

| - 2+ 2-
60H +4Pb +S0~3PbO.PbSO~.H20+21--Iz01
, solution
P~ 1, J,_ ps-
(~ mPU;mSO~-~-m b U,t
t

Q kb2++ S!4z- PbS04 I i I v

~) mPS+2me~rnPb (:~ rnSO~:.2mH+=mHz_~l
1 i
plate setution I
plate I
@2H§
+ I

Fig. 5a. Diagram of the elementary chemical and electrochemi- Fig. 5b. Diagram of the elementary chemical and electrochemi-
cal reactions with PbO as starting material, cal reactions with 3PbO" PbSO4" H20 as starting material.

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 858 J. Electrochem. Soc.: E L E C T R O C H E M I C A L S C I E N C E A N D T E C H N O L O G Y
3 P b O 9 P b S O 4 9 H 2 0 + 8e + 6 H +
-- 4Pb + SO42- + 4 H 2 0
E ----0.030 -- 0.044 p H -- 0.007 log aso42-
W h e n lead oxide and tribasic sulfate are consumed
in the paste or are located at a distance which does not
ensure a flow of P b 2+ ions toward the electrode sur-
face a n d which could participate in the electrochemical
reactions [1'] a n d [1"], reduction of the lead sulfate
begins. This process m a y take place provided the elec-
trode potential is more n e g a t i v e t h a n the e q u i l i b r i u m
potential of the Pb/PbSO4 electrode
P b S O 4 -5 2e = P b -5 SO4 2-
E = - - 0 . 3 5 6 -- 0.029 log aso42-
Sulfuric acid originates as a result of the reduction of
lead sulfate and diffuses back into the bulk of the elec-
trolyte.
The electrochemical reaction takes place at those
locations of the lead zone which are in contact with
lead compounds forming with lead electrodes with the
most positive equilibrium potentials. These are the
electrochemical reactions [1'a] and [1"a] which take
place until the eighth hour of formation. W h e n P b O
and 3 P b O 9 P b S O 4 9 H 2 0 are consumed, reaction [l"'a]
will take place and lead sulfate will be reduced.
Lead ions are consumed w h e n the electrochemical
reaction takes place in the solution layer at the
boundary with the lead crystals. In order to maintain
the electroneutrality of the solution in the pores of the
plate, in this layer the consumption of the positive
charges of the P b 2+ ions must be compensated. This
m a y be achieved by migration of H + ions from the
bulk of the solution toward this layer and of sulfate
ions in the opposite direction. These flows control the
advance of the lead zone along the thickness of the
plate. If the migration flows are hindered at a given
place in the plate, the pore solution there is charged
negatively by SO42- and O H - ions. This decreases the
rate of the electrochemical reaction P b 2+ + 2e ----P b
since the n u m b e r of negative ions at this place in-
creases. This decreases the rate at which the lead zone
advances along the cross section of the plate. The
migration flows are largest at the surface of the plate.
Hence, the lead zone advances first along the two sur-
faces of the plate, and only after having covered them
continues toward the bulk of the plate.
Evolution of the Pore Structure of the Plate during
Formation
By following the changes i n phase composition d u r -
ing formation one can determine the way in which the
volume fraction of the plate occupied b y m a t t e r is
built up. The plate shows good w o r k i n g parameters
w h e n there is a m a x i m u m access of sulfuric acid to
lead. This is achieved w h e n the active mass is very
porous. Such a structure originates d u r i n g plate forma-
tion. It is therefore desirable to determine the influence
of the formation processes on the b u i l d i n g up of the
porous structure of the active mass. Table I gives the
densities and the molar volumes of lead and of the lead
compounds present in the plate (16). F r o m Table I it
can be seen that there is a considerable difference i n
the molar volumes of lead and lead compounds.
Table II gives the changes in the molar volume d u r -
ing certain chemical and electrochemical reactions. The
Table I.
Molar v o l u m e ,
Compound Density, g/cm~
Pb 11.34
PbSO~ 6.23
P b O oft. 9.64
P b O tet. 9.36
3 P b O . PbSO~' ~ 6.60
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July 1974
Table II.
Reactions R e l a t i v e v o l u m e change
[l"a] w i t h respect to the
Starting product End product initial product, %
PbO Pb -- 23
3PbO'PbSO~-H20 + 60
PbSO~ + i00
3PbO.PbSO~.H20 Pb --52
PbSO4 + 23
PbSO4 Pb -- 60
[l'"a]
molar volume increases d u r i n g all reactions of sulfa-
tization of lead oxide and tribasic sulfate. I n all electro-
chemical reduction reactions the same volume de-
creases.
The porosity of the active mass is expressed b y two
parameters: total porosity and pore size distribution.
The changes in these parameters in the surface and
bulk portions of the plates were followed d u r i n g for-
mation. The samples for these m e a s u r e m e n t s were
t a k e n and dried together with the samples for the
phase composition studies.
The m e a s u r e m e n t s of total porosity and pore size
distribution were carried out with a Carlo Erba 65 AG
m e r c u r y porosimeter. The formation of lead amalgam
was avoided by creating a t h i n stearic acid film (17).
The samples from the surface and b u l k portions were
soaked in a 1% stearic acid solution in chloroform for
6 hr. They were t h e n t r a n s f e r r e d to watch glasses and
dried at 105~ A d e t e r m i n e d a m o u n t of m a t e r i a l was
weighed and introduced in the glass cell of the poro-
simeter. The results obtained are given in Fig. 6. The
curves of the surface and i n t e r n a l portions of the plates
are plotted and compared with that of the u n f o r m e d
plate.
These m e a s u r e m e n t s show that u p o n formation of
the negative plate the pore radii and the total !corosity
increase. Prior to formation the pore radii r a n g e b e -
t w e e n 0.1 and 0.3~. After formation, the tcore radii vary
b e t w e e n 0.6 and 8~, with a p r e d o m i n a t i o n of 1-4~
pores. The active mass has a porosity about 15% larger
t h a n that of the u n f o r m e d plate. However, if we take
into account the data of Table II, it becomes clear that
this value is too low. This discrepancy is caused b y the
f r a g m e n t a t i o n of the samples d u r i n g preparation. The
fragments b r e a k down at the locations of the largest
pores where the active mass is most brittle. These pores
are thus lost in the m e a s u r e m e n t .
Two stages m a y be recognized in the evolution of
total porosity. During the first one (until the sixth
hour) the total porosity of the surface decreases. This
indicates that the chemical reaction products predomi-
nate over the electrochemical reaction products. D u r i n g
this stage the porosity in the interior of the plate re-
mains constant. This shows that the effect of the sul-
fatization reactions is compensated for b y the effect of
lead formation. D u r i n g the second stage the total
porosity both of the surfaces a n d of the i n n e r parts
increases. This is connected with the reduction of lead
sulfate.
From Fig. 6 it can be seen that at the b e g i n n i n g of
formation, part of the pores decreases in radius. These
pores are located at those points of the paste where
only chemical sulfatization reactions have t a k e n place.
From Table I it is seen that the molecular volume of
the products (lead sulfate and tribasic lead sulfate) is
larger t h a n that of the starting compounds (lead
cm3/mole
oxide). On the other hand, at the exterior of the plate,
where a lead zone has formed, the pore radius has
12.28
47.96 increased (Fig. 2h). With the advance of formation the
29.15 lead zone increases, as does the pore radius. U n t i l the
23.88
152.00 sixth hour, this effect is larger at the surface parts t h a n
 Vol. 121, No. 7 LEAD-ACID BATTERY NEGATIVE PLATES 859

10 10

8 8

6
~ ~ 2h
~6 /71oh 9
4

~ 0 I I I I "- 0
"13
~n.,, ~o 10
r

V 8

'! 6 / / T2h
//,,C ,h
2

~= 0 o t i t
"- lO

o
= 8 ,o _o ~ ' - - ._.~,'
g of / ~ ' ~ ' ' ~
'- 6 o 6

4 o//
2

E 0 0' I
oJ o,~ 1 5 a
o10

8 Fig. 6b. Continuation of Fig. 60. Subsequent change in the pore

4
0 J I I
0.1 0.~ ~ s
Fig. 6a. Change in pore size distribution and volume porosity
until the eighth hour of formation.
i n the bulk. This is i n good accord with the results of
the phase composition studies.
F r o m Fig. 6 it is seen that at the eighth h o u r of for-
m a t i o n the pore size distribution in the interior of the
plate becomes identical with that of the surface parts.
It can be assumed that after this m o m e n t the reaction
of formation of lead at the surface and i n the b u l k
takes place at the same rate. Hence, the pore size dis-
t r i b u t i o n curves after the eighth hour have the same
shape.
Eiectrocrystailization Processes during F o r m a t i o n
of the N e g a t i v e Plate
F r o m the consideration of the e l e m e n t a r y chemical
and electrochemical reaction mechanism it becomes ap-
parent that the evolution of the lead active mass takes
place i n two stages. D u r i n g the first stage the lead
crystals are formed at the expense of dissolution of
lead oxide and tribasic sulfate. The crystallization
size distribution and volume porosity after the eighth hour of
formation, e , Unformed plate; O , at the surface of the plate; X,
in the bulk of the plate.
process occurs at a pH of the pore solution higher t h a n
that of the b u l k solution b u t lower t h a n 6 (the upper
limit of stability of lead sulfate). D u r i n g this stage a
n e t w o r k of lead crystals is built up. This n e t w o r k be-
e gins from the grid members, grows first at the surface,
and then in the interior of the plate. This lead n e t w o r k
includes lead sulfate crystals. The growth of the lead
crystals is controlled b y the flow of lead ions which
arrive from the lead oxide and tribasic sulfate which
are being dissolved. At a defined thickness of the plate,
paste density, and m a n u f a c t u r i n g technology conditions
can be created which could ensure a directed growth
of the lead crystals from the surface towards the center
of the plate. Such a m i c r o s t r u c t u r e of the active mass
has been observed (14).
During the second stage the lead sulfate crystals are
reduced. They are dissolved and P b 2+ ions lose their
charge on the p r i m a r y n e t w o r k of lead crystals. This
process occurs at a pH of the pore solution smaller t h a n
that of the b u l k solution. This gives rise to the sec-
o n d a r y structure of the active mass. It m a y be con-
cluded that the b u i l d u p of the active mass of the n e g a -
tive plate depends on c u r r e n t a n d paste density, sul-
furic acid concentration i n the electrolyte, and t e m -
perature. The d e t e r m i n a t i o n of the effect of each of
these i n d i v i d u a l parameters is of particular interest
since it will w i d e n and increase our knowledge of the
e l e m e n t a r y processes which take place u p o n formation
of the negative plate.
Manuscript received Jan. 22, 1974.

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 860 J. Electrochem. Soc.: E L E C T R O C H E M I C A L S C I E N C E A N D T E C H N O L O G Y J u l y 1974

A n y discussion of this p a p e r will a p p e a r in a Discus- chem. P o w e r Sources, 5, 21, (1970). (Published

sion Section to be published in the J u n e 1975 JOURNAL. b y Energia, Leningrad.)
A l l discussions for the J u n e 1975 Discussion Section 9. V. V. N o v o d e r s h k i n and G. I. Manoim, ibid., 1, 36
should be s u b m i t t e d b y Feb. 1, 1975. (1966).
1O. J. R. Pierson, P. Gurlusky, A. C. Simon, and S. M.
REFERENCES Caulder, This Journal, 117, 1463 (1970).
1. E. Willihnganz, National L e a d C o m p a n y Research 11. E. F. Bordt, G. A. Kolinova, V. V. Novodershkin,
L a b o r a t o r y Report, M a y 1940 Meeting of N a - and M. A. Dasojan, Pap. Electrochem. Power
tional B a t t e r y M a n u f a c t u r e r s Association. Sources, 7, 55 (1972). (Published b y Energia,
2. E. Willihnganz, Trans. Electrochem. Soc., 92, 281 Leningrad.)
(1947). 12. A. C. Simon and E. L. Jones, This J o u r n a l , 109, 760
3. T. I. Popova and B. N. Kabanov, Zh. Prikl. Khim., (1962).
32, 326 (1959). 13. N. E. Bagshaw and K. P. Wilson, Etectrochim. Acta,
4. Ja. B. Kasporov, E. G. Yampol'skaya, and B. N. 10, 867 (1963).
Kabanov, ibid., 32, 326 (1959). 14. A. C. Simon, in P o w e r Sources 2, 1968, Proc. S i x t h
5. E. G. J a m p o l ' s k a y a , M. I. Ershova, I. I. Astakhov, Intern. Symp., Brighton, D. H. Collins, Editor, p.
and B. N. Kabanov, Electrokhimiya, 2, 1327 33, P e r g a m o n Press, New Y o r k (1970).
(1966). 15. D. Pavlov, Proc. Symp. Batteries for Traction and
6. S. C. Barnes, Proc. Intern. ConS. Lead, 2nd, A m - Propulsion, p. 135, Columbus Section of The
hem., Oct. 4-7, 1965. Electrochemical Society (1972).
7. W. Simon, Bosch. Techn. Bet., 1, 234 (1966). 16. J. Burbank, This Journal, 113, 10 (1966).
8. L A. Agouf, M. A. Dasoyan, L. A. Ivanenko, E. V. 17. M. Svata, "Porosimetrie a j e j i pouziti," Czech.
Parshikova, and K. M. Solov'eva, Pap. Electro- Acad. Sci., p. 94, P r a h a (1969).

Impurity Effects in the Dissolution of Anodic Tantalum Oxide

J. P. S. Pringle*
Chalk River Nuclear Laboratories, Atomic Energy of Canada Limited, Chalk River, Ontario, Canada
The publication costs oS this article have been assisted by Atomic Energy of Canada Limited.

ABSTRACT
Anodic t a n t a l u m oxide dissolves slowly and u n i f o r m l y in h y d r o g e n fluoride
almost s a t u r a t e d w i t h a m m o n i u m fluoride. W h e n the oxide is i m p l a n t e d w i t h
h e a v y ions at fiuences of a r o u n d 1016/cm2, the dissolution accelerates; i m -
p l a n t e d w i t h the same fluence of hydrogen, it decelerates. S i m i l a r effects h a v e
been r e p o r t e d in the l i t e r a t u r e for i m p u r i t i e s i n c o r p o r a t e d from the e l e c t r o -
l y t e during anodization, and so the changes in the dissolution rate can be
ascribed to the physical presence of the impurities themselves. A c c e l e r a t e d
dissolution can be c o r r e l a t e d w i t h the concentration profiles of i m p l a n t e d
atoms. This provides a new m e t h o d for m e a s u r i n g the latter, and one t h a t is
p a r t i c u l a r l y useful for elements, such as neon, which have no l o n g - l i v e d
radioisotopes. The n a t u r e of the accelerating process could not be d e t e r m i n e d
owing to limitations in d a t a a n d analysis.

Anodic t a n t a l u m oxide dissolves slowly and v e r y
u n i f o r m l y in concentrated m i x t u r e s of hydrofluoric
acid and a m m o n i u m fluoride. Thin u n i f o r m l a y e r s can
t h e r e f o r e be r e m o v e d in succession, and this forms the
basis of a sectioning technique (1) for m e a s u r i n g the
r a n g e profiles of i m p l a n t e d r a d i o a c t i v e ions (2). I m -
plantation, however, is accompanied b y r a d i a t i o n
damage, and the l a t t e r is k n o w n to change the p r o p e r -
ties of materials. To ensure the precision of t h e m e a -
surements, therefore, it was n e c e s s a r y to find out
w h e t h e r i m p l a n t a t i o n affected the oxide dissolution.
E x p e r i m e n t s w i t h stable isotopes, p e r f o r m e d at flu-
ences of 1016-1017/cm2, showed that indeed it did (3).
The i m p l a n t a t i o n of h y d r o g e n slowed t h e dissolution,
b u t the i m p l a n t a t i o n of o t h e r elements accelerated it.
This difference b e t w e e n h y d r o g e n and o t h e r implants
i n d i c a t e d t h a t r a d i a t i o n d a m a g e was not responsible
for the changes in dissolution rate. F u r t h e r confirma-
tion was supplied b y reanodizing i m p l a n t e d samples to
g r e a t e r thickness. The anodizing c u r r e n t is thought to
flow t h r o u g h the oxide b y t h e simultaneous r e a r r a n g e -
m e n t of a n u m b e r of atoms, both t a n t a l u m and oxygen,
to n e w positions (4, 5), so that a n y s t r u c t u r a l changes
due to r a d i a t i o n d a m a g e should a n n e a l out. If t h e
change in dissolution r a t e remains, therefore, it m u s t
be a t t r i b u t e d to the continued presence of the i m -
p l a n t e d species. E x p e r i m e n t s w i t h i m p l a n t e d r a d i o -
. Electrochemical Society Active Member.
K e y words: tantalum, anodic oxidation, ion implantation, oxide
dissolution, impurity effects.
active k r y p t o n a n d copper show t h a t this is precisely
w h a t happens; on reanodization, the k r y p t o n stays in
the oxide and t h e accelerated dissolution effect stays
w i t h it, while the copper m i g r a t e s out of the oxide en-
tirely, and no accelerated dissolution is o b s e r v e d (3).
I m p u r i t i e s incorporated from the solution d u r i n g anod-
ization, should t h e r e f o r e b e h a v e similarly, and this is
indeed observed.
Effect of Impurities Incorporated during Anodization
Radioactive 32p and 3~S are found in the outer l a y e r s
of films f o r m e d in p h o s p h a t e a n d sulfate electrolytes
containing ~ 2 p o 4 - - - and 35SO4-- (6, 7), and n u c l e a r
microanalysis has shown that n i t r o g e n is i n c o r p o r a t e d
from nitric acid electrolytes (8). Though t h e r e is no
definite proof that these i m p u r i t i e s are present as the
oxyanions, this seems p r o b a b l e in view of the o x y g e n
analyses b y Amsel et al. (8). N a t u r a l l y , the a m o u n t of
i m p u r i t y i n c o r p o r a t e d varies w i t h the e x p e r i m e n t a l
conditions and is v e r y small in the dilute aqueous elec-
t r o l y t e s n o r m a l l y used (6, 1). I n c o n c e n t r a t e d e l e c t r o -
lytes, however, it can be large. Anodic films f o r m e d in
these electrolytes are scarcely oxides, and t h e i r p r o p -
erties are indeed significantly different. The difference
is, however, r e s t r i c t e d to the o u t e r layers of t h e f i l l
containing the impurity, since the i n n e r l a y e r s a p p e a r
to be similar in all respects w i t h films f o r m e d in dilute
electrolytes (6, 9, 10).
Accelerated dissolution of these o u t e r l a y e r s in H F
reagents has b e e n observed for films f o r m e d in con-

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