JOURNAL OF THE ELECTROCHEMICAL SOCIETY

ELECTROCHEMICAL SCIENCE
AUGUST
-- AND TECHNOLOGY
1973

A Model for Discharge of Storage Batteries

Dimitri Gidaspow
Institute 05 Gas Technology, Chicago, Illino{s 60616

and Bernard S. Baker*

Energy Research Corporation, Bethel, Connecticut 06801

ABSTRACT
The common porous electrode model has been rederived to include the
t r a n s f o r m a t i o n of one solid phase into another, for example, lead into lead
sulfate. Differential mass balances for the solid porous reactant and the solid
product yielded new dimensionless groups which characterize the structural
changes that occur d u r i n g discharge or charge of storage batteries. Effects of
fraction of active material, exchange c u r r e n t and molar density ratios on
overpotential at a constant c u r r e n t were investigated numerically. The trends
agree well with the empirical correlation of Shepherd.

At the present time no comprehensive electrode
model exists for batteries of any kind (1-4). Discharge
data are related to discharge d u r a t i o n by p u r e l y em-
pirical equations of the type Int ~ C, w h e r e I is cur-
rent, t is time, and n and C are constants having no
physical significance, as for instance in a recent paper
on lead-acid batteries (5). A more comprehensive em-
pirical equation is that developed by Shepherd (6). It
takes into account the consumption of the active mate-
rial and in this respect is not p u r e l y empirical. Shep-
herd's equation correctly describes discharge curves for
m a n y batteries over a range of c u r r e n t densities. His
polarization coefficient and electrical i n t e r n a l resist-
ance, however, have no physical m e a n i n g because they
are some lumped parameters for two electrodes with
at first no electrical resistance in the metal or solution
phases (Eq. 7), with an afterthought correction for a
resistance (Eq. 8).
The first theoretical attempt at predicting overpoten-
tials as a function of time that can be applied to a
single electrode of a b a t t e r y has recently appeared (7).
The authors use the common, steady-state, one-dimen-
sional porous electrode equations combined with a
mass transport of an active species given b y a mass
transfer coefficient that must be determined empiri-
cally. To handle t i m e - d e p e n d e n t p h e n o m e n a D u n n i n g ,
Bennion, and N e w m a n (7) assume that their mass
transfer coefficient is some reasonable function of the
a m o u n t of active material present in a n y part of the
electrode. Their approach a p p a r e n t l y allows them to
predict a failure caused b y an i n t e r n a l mass transfer
limitation with a sparingly soluble reactant, although
they do not cite a n y e x p e r i m e n t a l studies in support of
their conclusions. Their model cannot predict failure by
blockage of pores that is c o m m o n l y observed in lead
acid batteries (1) and i n the recent study of c a d m i u m
electrodes (8).
I n this paper we are proposing a model that describes
the time variation of charge and discharge of a b a t t e r y
for given electrode kinetics and initial structure of
* E l e c t r o c h e m i c a l Society A c t i v e M e m b e r .
K e y w o r d s : porous electrode, solid-state reaction, current dis-
tribution, p o r e p l u g g i n g , m o l a r v o l u m e s , i n t e g r a l equation.
electrodes. The structure of the porous electrodes
changes with the state of charge or discharge, with
pores opening or closing depending on the molar
volumes of solid reactants and products. The shape of
our calculated overpotential vs. fractional capacity
utilized curves agree with Shepherd's correlations. A
q u a n t i t a t i v e comparison has not been made, because
his discharge data are for two electrodes and because
we found that structural parameters that are usually
different for the negative and positive electrodes m a r k -
edly influence the overpotential curves. We present
numerical results for constant c u r r e n t operation of a
single electrode of a battery.
As in the study of Dunning, Bennion, and N e w m a n
(7) we consider the electrode to be one dimensional.
We therefore do not consider effects such as shape
changes that are two or three dimensional. We also
present n u m e r i c a l results only for the case of linear
polarization which is claimed to be (9) valid for alka-
line n i c k e l - c a d m i u m batteries and should be valid in
general at low c u r r e n t densities. The principal con-
tribution of this paper is believed to be the analysis of
b a t t e r y failure b y chocking near the front of the elec-
trode.
Description of the Model
Consider generation of c u r r e n t in a porous electrode
such as treated b y Ksenzhek (10), Pschenichnikov (11),
and particularly by Tobias and co-workers (12, 13).
However, u n l i k e in the previous studies (7, 13), assume
that in the porous electrode a consumable solid-fluid
reaction takes place. The reaction could be the forma-
tion of lead sulfate in the positive plate of a sulfuric
acid lead b a t t e r y
PbO2 + 2H + + H2SO4 + 2e-* PbSO4 + 2H20 [1]
the reaction of lead in the negative plate
P b + SO4 = -- 2e-> PbSO4 [2]
or the reaction of c a d m i u m to form an insoluble prod-
uct in the c a d m i u m electrode
Cd + 2 O H - -- 2e--> Cd(OH)2 [3]

1005

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 1006 J. Electrochem. Soc.: ELECTROCHEMICAL SCIENCE AND TECHNOLOGY August 1973
I n each case, in a w e l l - d e s i g n e d electrode, the solid linear relation seems applicable. F o r (Vm--Vs)/
reagent, be it lead or cadmium, is sufficiently finely (RT/nF) < < 1 r e l a t i o n [8] becomes
dispersed to be accessible to the electrolyte. As the
reactions proceed to the right, t h e r e is less and less i=i0 ~ (Vs-Vm) [91
solid r e a g e n t to produce current. F u r t h e r m o r e t h e solid
products occupy considerably more space forcing the
electrolyte out of the electrode. The ratios of m o l a r A l t h o u g h a specific form of c u r r e n t - p o l a r i z a t i o n rela-
volumes of solid products to solid reactants for Eq. tion will be used in this study, the t h e o r y presented
[1]-[3] are 1.9, 2.7, a n d 2.3, respectively (14). This h e r e is not r e s t r i c t e d to a n y p a r t i c u l a r electrode k i -
causes a decrease of the effective conductivity of the netics.
electrolyte in t h e pores of the electrode and possible It was a l r e a d y shown by Gidaspow (15) that for the
blocking of the pores. reaction
To easily handle this physical reality, assume that A ( f ) - n -5 S ( s ) -- n(e) -->7 P ( s ) [10]
at a n y point in space in the electrode we have the fol-
lowing phases: the solid reactant, called S, the solid a mass balance on S yields the differential equation for
p r o d u c t called P, electrolyte, binder, and a m e t a l sup- t h e volume fraction of S
port that acts as a conductor which is electrically con- O,s ( iMsa ~
nected to a m e t a l backing. Such a continuum a p p r o x i - ps Ot ------ ~ 1 es [11]
mation should be valid for a w e l l - d e s i g n e d electrode
of a high surface area, as discussed by Gidaspow (15). w h e n the thickness of the electrode remains constant.
Then on an inert free basis the volume fractions of S,
S i m i l a r l y a mass balance on P y i e l d e d
P, and the electrolyte a d d up to one
1 [4]
O,p ( iMp,a )
r -5 ep -5 e = = ~s [12]
PP " 7 nF
A c u r r e n t balance on an element of volume A~x, as
shown in Fig. 1, is Since expansion or contraction occurred at the e x -
x + ~x pense of the fluid phase, the v o l u m e fraction of liquid
[IeA]zx + ~z = _ f iaesAdx [5] is obtained b y difference as
w h e r e i is the r a t e of production of c u r r e n t p e r unit 9 --- 1 - - eS - - ep [13]
a r e a b y chemical reaction and a is the surface to vol-
u m e ratio for the solid reagent. The c u r r e n t flux I is Initial distributions of S and P can be chosen to be
related to the electrical conductivity of the solution, K functions of electrode thickness. T h e y are ~so and ~PO.
b y Ohm's l a w Two b o u n d a r y conditions are n e e d e d for t h e second-
o r d e r differential Eq. [7]. A t the m e t a l backing, solu-
0gs tion ends. T h e r e f o r e at
I -- - - K [61
0x 8Vs
x = L, ' -- 0 [14]
w h e r e Vs refers to the voltage in the solution phase as Ox
for e x a m p l e in the m o d e l of N e w m a n and Tobias (12).
A p p l i c a t i o n of t h e m e a n v a l u e t h e o r e m s to [5] and t h e To c o m p a r e calculated results to discharge data, con-
usual limiting process yield the p a r t i a l differential sider the case of constant c u r r e n t discharge. Then for
equation for the solution potential a discharge c u r r e n t density Io, expressed on an inert
free basis, at the solution end we have at
~ (K, ~Vs ) 0gs
= iaes [7]
x = 0, --K~ = I0 [15]
Ox Ox 0x
In g e n e r a l i is a function of p o t e n t i a l differences and
concentrations in the fluid phases of reactants and The electrode o v e r p o t e n t i a l Vs(t,0) -- Vs(t,L) is one
of t h e quantities w e w a n t to obtain. Note that Vm does
products. F o r constant concentrations in the porous
electrode a c o m m o n l y (12) used form is not e n t e r into this p o t e n t i a l difference.
The case of p r e s c r i b e d p o t e n t i a l at x -- 0, w h e n u s -

i----i0 exp -- 2R'--'~(Vm--Vs) j ing the l i n e a r r e l a t i o n [9] corresponds e x a c t l y to the

case of a first-order reaction for concentration obtained
b y Gidaspow (15). A l l results p r e s e n t e d for concen-
t r a t i o n are applicable to the p o t e n t i a l difference in this
--exp[ nF ) case. However, since such operation is u n c o m m o n w e
'2RT ( V m - - Vs) ] [8]
will proceed only w i t h the constant c u r r e n t case. The
m o d e l is, of course, a p p l i c a b l e to t i m e - d e p e n d e n t opera-
w h e r e i0 is the exchange c u r r e n t density, Vm the m e t a l
tion, as long as changes are slow enough for the
potential, and the other symbols have their usual m e a n -
d o u b l e - l a y e r c a p a c i t y effects to be negligible. Changes
ing. Sometimes (6) for discharge of storage batteries a
in concentration can be accounted for by t h e use of
diffusion equations of the t y p e solved b y G i d a s p o w
(15) coupled w i t h the p r o b l e m p r e s e n t e d here. W h e n
t h e m e t a l r e a g e n t carries most of the current, an e q u a -
tion for m e t a l p o t e n t i a l of the t y p e of Eq. [7] m u s t be
a d d e d to t h e system. In this study, however, the con-
SOLUTION d u c t i v i t y of the m e t a l phase is assumed to be so high
t h a t the m e t a l is at t h e potential of the m e t a l backing
plate.
We w o u l d like to add t h a t w h i l e potentiostatic studies
of b a t t e r i e s are rare, as a l r e a d y noted b y S a n g h i and
F l e i s c h m a n n (16), t h e y p r o v i d e an e x c e l l e n t m e a n s to
s t u d y rates of electrochemical reactions. Since the r a t e
constants controlling electrochemical reactions are
x--O x=L chiefly potential dependent, t h e y can be k e p t constant
d u r i n g s t u d y b y this procedure. I n this w a y we obtain
an a n a l o g y b e t w e e n concentration and potential. W e
A-IIII166 thus e x p e c t the rates to b e h a v e s i m i l a r l y w i t h potential,
Fig. 1. One-dimenslonal porous electrode with a consumable solid as was o b s e r v e d w i t h concentration b y Onischak a n d

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 Vol. 120, NO. 8 MODEL FOR DISCHARGE OF STORAGE BATTERIES 1007

Gidaspow (17). I n d e e d F l e i s c h m a n n and Thirsk's (18) Then using both b o u n d a r y conditions we obtain
Equation 1 is analogous to Gidaspow's Equation 12
(15). F u r t h e r m o r e , F l e i s c h m a n n and Thirsk observed
m a x i m a in rates w i t h time for the reverse reaction
@2 s ~sYdx' = I [25]
given by Equation 2 for which pores tend to open up
leading to an initial increase in rate. Such limited elec- Equation [25] says t h a t we d r a w c u r r e n t at a constant
trochemical rate studies w i t h consumable solid re- rate. Using this equation and a p p l y i n g an i n t e g r a l of
actions p r o v i d e additional support for the form of the zero to one to Eq. [23], C2 is d e t e r m i n e d to b e
r a t e expression chosen in this study. 1
DimensionlessEquations
For the case of linear polarization, as expressed b y y : ~sdx'
Eq. [9], the potential d i s t r i b u t i o n in the electrode is i x I
governed b y + [20]
0 ( 0Y)
0x ' O--~ = r [161
E q u a t i o n [23] is now a functional e q u a t i o n of the form
I n Eq. [16], Y is the difference of solution minus m e t a l Y ----G (Y) [27]
potentials scaled by t h e c u r r e n t drawn, as shown below
It is solved s i m u l t a n e o u s l y w i t h t h e i n t e g r a l Eq. [21]
Vs- Vm b y iteration and m a r c h i n g in time s i m i l a r l y to the pro-
Y - [17] cedure a l r e a d y discussed b y G i d a s p o w (15). As a first
guess in the iteration p r o c e d u r e the exact a n a l y t i c a l
K / solution for zero time, shown in the n e x t section, was
used. In this m a n n e r the simple i t e r a t i o n
The b o u n d a r y condition given b y Eq. [15] d i c t a t e d this
choice of scale factor. Yn+l ----G ( Y , ) [28]
The g r o u p
ionFaL 2 w h e r e the subscripts denote iterates w o r k e d for p a -
r = [18] r a m e t e r s investigated in this study. I m p r o v e d iteration
RTK was only i n f r e q u e n t l y r e s o r t e d to.
is a dimensionless e x c h a n g e current. It is called r due The fraction of t h e o r e t i c a l capacity utilized, tf, can
to its analogy to the Thiele modulus in the concentra- be obtained from the dimensionless time, t, using the
tion p r o b l e m (15). relation t ---- e s o r d e r i v e d in the previous section. It
The b o u n d a r y conditions (BC) for Eq. [16] become, can be also obtained b y m a t e r i a l balance as follows. By
in dimensionless form definition w e have
OY (t,1) OY (t,O) Yl 'SO -- eS
BCI:----O BC2: e---- 1 [19] tt -- dx [29]
O~ a~ eso
Equation [11] dictates that the dimensionless time, Substitution of Eq. [21] gives
be expressed a s
{ = ( ioMsaL 2/ IotMs tt = l -- y : exp [ -- j ~ Ydt ] d x [30]
) ( ot) = ,sob ,soC snF/= ,sor [2o]
with Such a calculation served as a check on possible ac-
tf = Iot/Q c u m u l a t i o n of errors. It was obtained in a n a t u r a l w a y
from the q u a n t i t y of solid p r o d u c t formed, given at a n y
w h e r e t4 is the fraction of theoretical capacity utilized x b y the equation
at time t, since Q -- ,so LpsnF/Ms is the initial n u m -
b e r of coulombs p e r unit area of electrode on an inert 'P -- ' P O = E (eso -- 'S) [31]
free basis. Discharge d a t a are u s u a l l y plotted vs. I 0 t
or vs. Iot/Q. The fractional capacity utilized calculated in this man-
I n Eq. [16], ,s is d e t e r m i n e d b y the i n t e g r a t e d form ner always agreed with that calculated from the di-
of Eq. [11] which is mensionless time, t. To minimize expenditure of com-
puter time, the interval zero to one was divided into
,s=esoexp [--y~oYdt ] [21] only ten or twenty parts, since the computer time in-
creased as the cube of the ratio of subdivisions. With
a n d , is given b y
ten subdivisions it took only a few minutes on the small
9= ( 1 - - E e s o - - ,PO) + (E -- 1)es [22] I B M 1130 to generate a complete time profile.For small
r results were sufficiently accurate for graphical rep-
w h e r e E is the ratio of m o l a r volumes of solid p r o d u c t resentation even with such a coarse grid.
to solid r e a c t a n t times the stoichiometric coefficient 7.
Integral Equation Representation Zero Time Solution
To solve this n o n l i n e a r system of p a r t i a l differen- A t zero time, t h a t is before a n y capacity of the bat-
tial equations it is best to r e f o r m u l a t e the system in t e r y is used up, the system of p a r t i a l differential equa-
terms of i n t e g r a l equations. I n t e g r a t i o n of Eq. [16] tions reduces itself to the simple b o u n d a r y value prob-
using b o u n d a r y condition [2] gives lem
f Z dz IoZ Yesdx'--I x --e
l dz + C2 [23] _ _ = d 2 y r ,so y
y -- r ~ o ~ d~ '~ ,0

w h e r e C~ is an integration p a r a m e t e r . To obtain C2 ap- dY(1) dY(0)

p l y an i n t e g r a l of zero to one to Eq. [16]. This pro- BCI: ~ = 0 BC2: ,o~----i [32]
d~ d~
c e d u r e gives
where
9
alYa]x o - - r 2 ~ , s Y d x ' [24] eO ~- 1 - - , S O - - epo
Its solution is

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 1008 J. E l e c t r o c h e m . Soc.: ELECTROCHEMICAL SCIENCE AND TECHNOLOGY August 1973

1 % DISCHARGE
Y = cosh Cx~/,so/,0
r t a n h r EVr~'/eo 0.5

1
sinh Cx~/eso/,0 [33] zo
I
~" 0.4
By Taylor series expansion we can obtain some useful
approximations. Equation [33] shows that for small r
that is for t h i n cells, Y becomes very large. Y is
r o u g h l y given b y 1/r -- x / , o -- x2/~o. This shows
that for small r we m u s t obtain Y correct to a large 0.~,
n u m b e r of significant figures in order not to lose all
accuracy in calculating the potential difference Y (0)
- - Y(1). This overpotential can be approximated b y
the f o r m u l a 5 0.2
1 ('-- 1 ) h
Y(0) -- Y(1) = 2--~" -~--r [34]
for
r < 1 0 OJ

F o r m u l a [34] shows that for r < 1 and reasonable

,so, the overpotential is not a function of the electrode 95
kinetics. Roughly we have
Vs(0,0) -- Vs(0,L) 1 O.F 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 I.O
= ~ [35] DIMENSIONLESS ELECTRODE THICKNESS,'f=x/L
IoL 2,0
Fig. 2. Distribution of active material during discharge

The electrode kinetics which appears in the d i m e n s i o n - % DISCHARGE

less exchange c u r r e n t r is only a correction to the O
d o m i n a n t behavior which is governed by the conduc- 0.5

tivity and the structure of the electrode. Values of 20

r much larger t h a n one result in a high localization of
the reaction near the solution face and are not desir-
able. Such cells are m u c h too thick. A value of r near 0.4
one is not u n r e a s o n a b l e as seen from the hypothetical
example below. Let
i0 = 10 -~ A / c m 2 nF
-- 40 volts-* . 0.5
a ---- 104 cm -1 RT Z ~
_O 95
K ---- 10 -1 m h o / c m L -- 0.1 cm
Then r becomes equal to 0.4. Note that by having 1.5 5 0.5
Q 0.2 - -
chosen a simplified form of polarization relation we ~> - - - - - - 2.5 0.5 0.5
were able to obtain a n u m b e r of significant conclusions
5O
which may have escaped us had we tried to solve a
more realistic p r o b l e m at the start. /

Numerical Resultsand Discussion

Several kinds of i n f o r m a t i o n can be derived from the /
model. I n Fig. 2 the distribution of reactant is shown as /
a function of electrode thickness for different states of 0 / I I I I I I I I I
discharge starting with zero for reference purposes and O O.r 0.2 0.3 0.4 O.5 0.6 0.7 0.8 0.9 LO
rising to 95% discharge. We assumed there was no solid DIMENSIONLESS ELECTRODE T H I C K N E S S , ~ = x / L
product initially for all cases studied and chose the
Fig. 3. Distribution of electrolyte with incomplete ( ) and
values of E and ,so such that pores n e v e r u l t i m a t e l y
complete ( - - ) pore closing.
close completely. In Fig. 3 the void fraction distribu-
tion is indicated b y solid lines for this case. The voids
are filled with electrolyte in the model and therefore tive and positive electrodes. Specifically Shepherd's
the curves indicate how the electrolyte conductivity Equation 8 can be r e w r i t t e n in our notation as
changes with depth into the electrode. The dashed
Vs (t,0) -- Vs (~,L) 1
curves in Fig. 3 are for such a sufficiently high value - - - - -4- N / K s h [36]
of E that pores u l t i m a t e l y close. This leads to incom- IoKsh I0t
plete discharge. Only slightly over 56% of the theo- Q
retical capacity can be utilized w h e n half the volume
of the electrode on an inert free basis is m a d e of the where Ksh is the K used by Shepherd and N is his N.
active material. Clearly such an electrode should never The left side of Eq. [36] corresponds to our d i m e n s i o n -
be built and those with experience in the field avoid less overpotential in the plots. The i n d e p e n d e n t vari-
the use of such high percentages of active solid mate- able is identical with Shepherd's. Our plots have the
rial. basic shape indicated by Eq. [36], except that Shep-
Constant c u r r e n t b a t t e r y discharge data with respect herd's correlation predicts an infinite overpotential for
to a reference electrode can be obtained in the labora- complete utilization only. Our model predicts high
tory as a function of discharge time. Figures 4-6 show overpotentials for less t h a n complete utilization, for
such overpotentials vs. discharge times for various hy- poorly constructed electrodes.
pothetical electrodes. We note that the plots agree with Figure 4 shows the large effect played b y the ex-
the empirical correlation of Sheperd (6), as much as pansion ratio, E. The values indicated are quite r e a l -
one can expect of a correlation that averages the n e g a - istic, since E for the negative plate of a sulfuric acid

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 Vol. 120, No. 8 MODEL FOR DISCHARGE OF STORAGE BATTERIES 1009
12

I0--
, .oo i i 9
,so=0.5 0.5
~ A 9
"~1~
o.l :
~r I 8
J
j" 7 ,3_ 7
I-
r-
z 6 g ~
hi
e~

(E 5 E 25 E 20 N 5
O
DJ
>
0 uJ
.j 4 ~ =O . y
(D z
Q ,so = .
.J
Z 3 3--
o
(D a
Z ~t =0.01 LINE
hi 2 j @Z=0.0 I
,So=0.35
I I

o0 I I I I I I r I I o I I I I I I I I J
O 0.1 O.2 03 04 0.5 0.6 0.7 08 09 t.O
0.~ 02 0.3 0.4 0.5 0.6 0,7 0,8 0.9 ,0
FRACTIONAL CAPACITY UTILIZED, tf= (Iol)/((soLpsnF'/M s )
FRACTIONAL CAPACITY UTILIZED, lot/Q
Fig. 6. Effect of dimensionless exchange current, r on overpo-
Fig. 4. Effect of expansion ratio on overpotential
tential for two initial fractions of active material.

b a t t e r y is 2.7. Thus if half the plate w e r e m a d e of
lead (eso ---- 0.5 in the figure) no m o r e than about 30%
of the theoretical capacity could be utilized.
F i g u r e 5 shows the effect of the initial fraction of
active m a t e r i a l on overpotential. For a u n i f o r m l y ac-
cessible case (15) pores will close completely w h e n
the product of eso and E reaches unity. F o r E _-- 2.5
in Fig. 5 this occurs at ~so ---- 0.4. The p e r f o r m a n c e of
the hypothetical b a t t e r y shown is poor at this v al u e
and beyond. No one w o u l d build such a plate. O u r re-
sult, however, has nothing to do w i t h hard w o n ex -
perience. The a g r e e m e n t with the facts shows the
validity of the transport p h e n o m e n a approach.
6 by the results presented by Gidaspow (15) for concen-
iM , b a t t e r y electrodes and analyzed as suggested by the
4 fso = 08 9so=0 6 9so =05
I A
0 I
0 0.1 0.2 0.3 0.4 0.5 0.6
FRACTIONAL CAPACITY UTILIZED, I o t / Q
Fig. 5. Effect of initial fraction of active material on overpoten-
tial with a high expansion ratio, E, and unit dimensionless ex-
change current, r
F i g u r e 6 shows the effect of the dimensionless ex-
change c u r r e n t on overpotential, that is it shows the
role played by the electrochemical kinetics. In the
linearized polarization cu r v e real kinetics entered only
t h r o u g h the exchange current, i0. In dimensionless
quantities it appeared only in r F i g u r e 6 shows that
at least for values of r less than one electrochemical
kinetics plays only a small role. To v e r i f y this sur-
prising conclusion w e had developed the a p p r o x i m a t e
solution for zero t i m e p r esen t ed in the previous sec-
tion. In v i e w of this result w e feel that our m o d e l ap-
p r o x i m a t e s the operation of a real battery.
Operation of t h e electrode at a constant overpoten-
tial, w i t h other assumptions held the same, is described
tration. Th e dimensionless p r o b l e m for a dimensionless
o v er p o t en t i al Y is given by his Equations 20 to 23. As
shown in his F i g u r e 3, the cu r r en t will decrease w i t h
time e x p o n e n t i a l l y w h e n pores close. We also suggest
that kinetic data that are needed for f u r t h e r refinements
of our model be obtained potentiostatically on real
models.
.4 Acknowledgment
P a r t i a l support for this study was provided by the
Basic Research P r o g r a m of the Institute of Gas Tech-
nology.
Manuscript submitted Oct. 24, 1972; revised m a n u -
script received March 9, 1973. This was P a p e r 18 p r e -
sented at the Miami Beach, Florida, Meeting of t h e
9 so =0.3
Society, Oct. 8-13, 1972.
A n y discussion of this p ap er will appear in a Discus-
sion Section to be published in t h e J u n e 1974 JOURNAL.
SYMBOLS
cross-sectional area of porous electrode, c m ~
a specific surface area of porous electrode (surface
to v o l u m e ratio) cm2/cm s
E expansion factor i n v o l v i n g a ratio of m o l a r vol-
umes, 7Mpps/MspP
F F a r a d a y ' s constant, 96,500 c o u l o m b s / e q u i v a l e n t
0.7 0.8 0.9 1.0 I apparent c u r r e n t density, A / c m 2
I0 constant c u r r e n t discharge density, expressed on
an inert free basis, A / c m 2
i true c u r r e n t density or rate of reaction e x p r e s -
sion, A / c m 2
i0 exchange c u r r e n t density, A / c m 2

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 1010 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 August 1973

K conductivity of electrolyte (see Eq. [6]), m h o / c m 2. R a y m o n d Jasinski, "High-Energy Batteries,"

Ksa constant K in Shepherd's correlation P l e n u m Press, New York (1967).
L thickness of electrode, cm 3. S. Uno Falk and A. J. Salkind, "Alkaline Storage
Mp molecular weight of P, g P / m o l e P Batteries," J o h n Wiley & Sons, Inc., New York
Ms molecular weight of S, gS/mole S (1969).
n u m b e r of electrons transferred in electrochemi- 4. J e a n n e Burbank, A. C. Simon, and Eugene Willi-
cal reaction hnganz, in "Advances in Electrochemistry and
N constant in Shepherd's correlation Electrochemical Engineering," Vol. 8, pp. 157-251,
Q initial capacity of electrode per unit inert free Wiley-Interscience, New York (1971).
area, esoLpsnF/Ms, coulombs/cm 2 5. P. E. Baike, M. I. Gillibrand, and K. Peters, Elec-
R ideal gas law constant trochim. Acta, 17, 839 (1972).
T absolute temperature, ~ 6. C. M. Shepherd, This Journal, 112, 657 (1965).
t time, sec 7. J. S. Dunning, D. N. Bennion, and J o h n Newman,
tf fraction of theoretical capacity utilized at time t, ibid., 118, 1251 (1971).
Iot/Q 8. P. Bro and H. Y. Kang, ibid., 118, 519 (1971).
tm time at which the pore closes, sec 9. O. G. Malandin, V. N. Kosholkin, A. G. Gerasimov,
and O. S. Ksenzhik, 7th Intersociety E n e r g y Con-
t dimensionless time, ioMsaLIot/RTKps : ~so~2tf version E n g i n e e r i n g Conference, S a n Diego,
VM potential in the matrix, V Calif., S e p t e m b e r 1972.
Vs potential in solution, V 10. O. S. Ksenzhek, in "Fuel Cells. Their Electrochemi-
x space coordinate in the direction of pores, cm cal Kinetics," p. 1, Consultants Bureau, New
x dimensionless length, x / L York (1966).
Y dimensionless potential : (Vs -- V m ) / ( I o L / K ) 11. A. G. Pshenichnikov, ibid., p. 11.
12. J. S. N e w m a n and C. W. Tobias, This Journal, 109,
Greek Letters 1183 (1962).
-y stoichiometric coefficient in Eq. [10], mole P / m o l e 13. R. C. Alkire, E. A. Grens II, a n d C. W. Tobias, ibid.,
S 116, 1328 (1969).
9 void fraction, cm 3 fluid/cm 3 total 14. R. C. Weast, Editor, "Handbook of Chemistry and
~p volume fraction of solid product P, cm 3 P / c m 3 Physics," Chemical R u b b e r Co., Cleveland
total (1971).
eo void fraction at zero time, cm 3 fluid/cm3 total
epo initial v o l u m e fraction of solid product P, cm 3 15. Dimitri Gidaspow, 7th Intersociety E n e r g y Con-
P / c m ~ total version E n g i n e e r i n g Conference Proceedings, pp.
es volume fraction of solid reactant S, cm 3 S / c m 3 1159-1168, A m e r i c a n Chemical Society, W a s h i n g -
total ton (1972). Also in "Recent Developments in
eso initial volume fraction of solid reactant S, cm 3 Separation Science," Vol. 2, pp. 59-70, N. N. Li,
S / c m 3 total Editor, Chemical R u b b e r Co., Cleveland (1972).
pp void free density of solid product P, g P / c m s P 16. I. Sanghi and M. Fleischmann, Electrochem. Acta,
ps void free density of solid S, gS/cm~ S 1, 161 (1959).
~2 dimensionless exchange c u r r e n t = ionFaL2/RTK 17. Michael Onischak and Dimitri Gidaspow, i n "Re-
(electrochemical Thiele modulus) cent Developments in Separation Science," pp.
71-93, N. N. Li, Editor, Chemical R u b b e r Co.,
REFERENCES Cleveland (1972).
1. G. W. Vinal, "Storage Batteries," 4th ed., J o h n 18. M. F l e i s c h m a n n and H. R. Thirsk, Trans. Faraday
Wiley & Sons, Inc., New York (1951). Soc., 51, 71 (1955).

The Hydrogen Evolution Reaction on Ti-6AI-4V

in Acidic Solutions of NaCI-HCI
Pedro J. Aragon
Facultad de Ciencias, Departamento de Quimica, Universidad de Los Andes, Merida, Venezuela

ABSTRACT
The HER on polyerystalline Ti-6A1-4V in acidic solutions of NaC1-HC1 at
constant concentration of C1- ---- 0.5M, and pH range from 0.65 to 2.5 was
studied. U n d e r the present e x p e r i m e n t a l conditions, the reaction was shown
to be first order with a Tafel slope of 0.153V. Exchange c u r r e n t densities were
in the order of 10 -8 A - c m -~. A n apparent energy of activation of ~E = 45.3
k e a l - m o l - I was found. A sharp decrease in potential was observed after
reaching about --1.220V (SCE). It is assumed that this effect is due to con-
centration polarization. Curves corresponding to cathodic polarizations showed
a positive deviation from linearity for pH 0.65 and 1.22, p r e s u m a b l y due to a
second reduction process corresponding to the reduction of a surface oxide film.

The alloy Ti-6A1-4V was investigated because of
its excellent corrosion and mechanical properties. Al-
though considerable work has been done on t i t a n i u m
and some of its alloys, only a few papers report on the
m e c h a n i s m of the HER on pure Ti (1, 2) and none on
Ti-6A1-4V.
Thomas a n d Nobe (1) investigated different concen-
trations of H2SO4 as the electrolyte solution. Hacker-
m a n and Hall (2), w o r k i n g in a p p r o x i m a t e l y n e u t r a l
Key words: hydrogen evolution, kinetics, titanium alloys, cor-
rosion.
solutions of NaC1 reported Tafel equations of E -- 1.93
~- 0.154 log i, and E" = 1.97 -p 0.204 log i for deaerated
a n d aerated solutions.
In this paper the kinetics of the HER on Ti-6A1-4V
at 25~ in NaC1-HC1 solutions, at constant c o n c e n t r a -
tion of C I - , and in the pH range 0.65-2.5 is reported.
Experimental
Several disks of Ti-6A1-4V1 with an area of 0.363
cm -~ and their Teflon holders were polished w i t h
x P r o v i d e d by T i t a n i u m Corporation of A m e r i c a , U.S.A.

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