Design of Primary and Secondary Ceils

II. An Equation Describing Battery Discharge

C. hA. Shepherd
U. S. N a v a l R e s e a r c h L a b o r a t o r y , W a s h i n g t o n , D. C.

ABSTRACT
A discussion is given of the derivation and application of an equation which
gives an excellent description of a wide variety of cell and battery discharges.
This equation gives the cell potential during discharge as a function of dis-
charge time, current density, and certain other factors. It makes possible a
complete description of cell discharge characteristics, using a minimum of ex-
perimental data and at the same time pinpointing experimental errors. It can
also be used to describe cell charges, capacities, p o w e r evolution, and to p r e -
dict capacities. A description is g i v en of a simple n u m e r i c a l m e t h o d f o r fitting
this equation to a p a r t i c u l a r set of b a t t e r y discharge curves. A graphical
m e t h o d is described for c o m p a r i n g characteristics of various types of cells.

This paper is one of a series w h o s e u l t i m a t e goal is w h e r e i is the a p p a r e n t c u r r e n t density in amperes

to d e t e r m i n e procedures for designing batteries h a v -
ing o p t i m u m properties such as m i n i m u m w e i g h t or
m i n i m u m volume. In particular, the d e r i v a t i o n and
application of an equation describing cell discharge
w i l l be discussed. T h e equation can be used to locate
variations in the discharge data due to e x p e r i m e n t a l
error, u n c o n t r o l l e d variables, etc., thus m i n i m i z i n g the
a m o u n t of e x p e r i m e n t a l data needed and cutting the
costs of evaluation. A complete set of discharge curves
can be described by a single equation, m a k i n g it
possible to p r e s e n t in less space a more detailed d e-
scription of cell characteristics than has been custom-
ary in m a n y b a t t e r y papers.
per square centimeter, io is the a p p a r e n t e x c h a n g e
c u r r e n t density in a m p e r e s p er square centimeter, a
is the transfer coefficient (0 ~ ~ ~ 1), Z is the n u m -
ber of electrons t r a n s f e r r e d in the r a t e - d e t e r m i n i n g
step, F is the Faraday, R is the gas constant, and T is
the t e m p e r a t u r e in ~ The s t e a d y - s t a t e activation
overpotential, ~1, is positive for the deposition of cations.
W h e n the e x p o n e n t i a l t er m s are e x p a n d e d as a
series, powers g r e a t e r than one can be neglected if
is sufficiently small and Eq. [1] becomes

Derivation and Determination of the thus establishing a l i n e a r relationship b e t w e e n ~ and i

w h i ch is f a i r l y accurate up to the values of n equal to
Discharge Equation a p p r o x i m a t e l y 0.03v. If Eq. [1] is applicable to a cell,
The mathematical analysis given here is based on the v a r i a t i o n of ~ w i t h change in i can be fitted by a
the assumption t h a t the following conditions are ap- straight line w i t h i n a p p r o x i m a t e l y 0.02-0.04v up to
plicable: (A). Th e anode a n d / o r cathode h a v e p o r - values of ~1 equal to about 0.2-0.4v. A potential drop
ous active materials. (B). The electrolyte resistance is of this m a g n i t u d e w o u l d cover the m a j o r portion of
constant t h r o u g h o u t discharge. (C). The cell is dis- the polarization that occurs d u r i n g most b a t t e r y dis-
charged at a constant current. (D). The polarization charges.
is a linear function of the active m a t e r i a l c u r r e n t d e n - In Fig. 1, two solid curves, ia and ib, are shown w h i c h
sity. r e p r e s e n t typical b a t t e r y discharges. T h e potential in
W h e n ionic discharge is the slow or rate d e t e r m i n i n g volts is plotted as a function of (it), the q u a n t i t y of
process, the relationship b e t w e e n s t e a d y - s t a t e c u r r e n t electricity that has been obtained f r o m the b a t t e r y
density and activation o v e r p o t e n t i a l at an electrode at t i m e t. It is assumed in the d e r i v a t i o n that follows
in a constant concentration e l e c tr o ly te is usually w r i t - that the polarization is linear to the right of point b
ten as and b'. If all factors except polarization are ignored,
i ~- toe a~zF/aT - - t o e --(1--a)~ZF/RT [1] then Ec, the cathode potential during discharge, is
defined as
Ec = E~c -- Kciam [3]
w h e r e Esc is a constant potential, Kc is the cathode
coefficient of polarization per unit active m a t e r i a l cur-
r e n t density, and ia,, is the active m a t e r i a l c u r r e n t
2 ia
b density. Th e successful use of Eq. [3] as a f u n d a m e n t a l
, equation in the d e r i v a t i o n that follows does not neces-
I
I 1
sarily i m p l y that the t h e o r e t i c a l factors associated w i t h
Eq. [1] apply to most b a t t e r y discharges e v e n though
both equations are linear.
! TANG~ LINE In the case of a porous electrode the active m a t e r i a l
~ c c u r r e n t density tam is defined as being i n v e r s e l y p r o -
'1 1 I 3~.,~f ~,1 VOLT I portional to the a m o u n t of unused active m a t e r i a l and
I is also equal to i at the b eg i n n i n g of the discharge.
i[ Ii i\ Consequently
II i i I
I I I I I
I
II.1 Ibtd ,I '] .~btf
I .
II iate Qc ~ it
tip / I I*"
ibt I iat2 ibt3 iat 4 w h e r e t is the time at any point d u r i n g the discharge
Jt (AMPERE~MLNUTES/CM2} and Qc is the a m o u n t of av ai l ab l e cathode active m a -
terial expressed in units such as a m p e r e hours p e r unit
Fig. 1. Typical discharge curves used in equation fitting area.

657
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 658 JOURNAL OF THE ELECTROCHEMICAL SOCIETY
W h e n Eq. [4] is substituted in Eq. [3]
Qc )i
Similarly
Ea : E s a - Ka
(Q~Qa -- it i [6]
where the subscripts a and c denote the anode a n d
cathode values for the constants, respectively. A sign
convention is used here which makes the value of the
potential terms positive.
If Qa is a p p r o x i m a t e l y equal to Qc, as it generally
is in a well designed cell, Eq. [5] a n d [6] can be
summed to give
where E = Ea + Ec is the potential of the cell (ne-
glecting the i n t e r n a l resistance) at a n y time t d u r i n g
the discharge; Es : Esa 27 Esc is a constant potential;
K = Ka 27 Kc is the polarization coefficient in ohm cm2;
and Q = Qa ~- Qc is the available a m o u n t of active
m a t e r i a l i n coulombs or similar u n i t s per u n i t area.
If Qa is appreciably larger t h a n Qc, then the n u -
merical increase in the value of the last term in Eq.
[6] will be small compared to the n u m e r i c a l increase
in the v a l u e of the last term of Eq. [5] as (it) ap-
proaches Qc in value. Consequently, the second t e r m
of Eq. [6] can be considered to be approximately con-
stant and the sum of Eq. [5] and [6] will still have
approximately the form shown in Eq. [7]. U n d e r these
conditions the approximate values of K, Q and Es will be
K -~ Kc, Q = Qc, and Es -~ Esa 27 Esc-- Kai. If Qc is a p -
preciably larger t h a n Qa, then the approximate values
of K, Q, and Es will be K ~ Ka, Q ~ Qa, a n d Es : Esa
27Esc -- Kci. Thus Q is d e t e r m i n e d b y the a m o u n t of
available active m a t e r i a l on the controlling electrode
which is the one that fails first. A similar a r g u m e n t
will show that the same type of equation will be ap-
proximately true w h e n several cells are connected in
series to form a battery.
W h e n the potential drop due to i n t e r n a l resistance
is considered, Eq. [7] becomes
E ~- Es -- K ( QQ) i - - N
it i -
where N, the i n t e r n a l resistance per u n i t area, is
measured in ohm cm 2 or other suitable units.
When Eq. [8] is evaluated mathematically, a set of
curves is obtained, one of which, plotted in Fig. 1, is
a dotted line from a to b and a solid line from b to c.
The initial drop in potential at the b e g i n n i n g of a cell
discharge is not included in Eq. [8]. Consequently
another term m u s t be added to correct for the differ-
ence b e t w e e n the dotted line potential calculated from
Eq. [8] and the solid line gb that represents the actual
discharge potential. It has been f o u n d that the expres-
sion A e x p ( - - B Q - l i t ) , where A and B are empirical
constants, gives an excellent estimate of the initial
potential drop in v i r t u a l l y every case. W h e n this t e r m
is added to Eq. [8], the final equation
E=Es--K( --Q )i--Ni27Aexp(--BQ-lit)
Q it
is obtained. I n a n u m b e r of cases the initial drop in
potential was too rapid to be included in the observed
e x p e r i m e n t a l data and consequently, the value of A exp
( - - B Q - l i t ) , being negligible, could be ignored.
That portion of the discharge curve that lies to the
right of point b in Fig. 1 could be predicted from
Eq. [9] if the n u m e r i c a l values of Es, K, Q, and N
were known, providing the basic assumptions were
true. However, the labor involved in d e t e r m i n i n g these
values would be so large that it p r o b a b l y would be
easier, and certainly more accurate, to determine dis-
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July 1965
charge curves experimentally. However, Eq. [9] can
be fitted n u m e r i c a l l y to e x p e r i m e n t a l discharge data,
[5] thus d e t e r m i n i n g empirical values of Es, K, Q, N, A,
and B. Such a n u m e r i c a l equation gives an accurate
description of the cell or b a t t e r y discharge and can be
used to describe energy evolution, cell capacity, and
can be used in predicting cell capacities. Despite its
successful applications, it m u s t be considered to be
a n empirical equation since the n u m e r i c a l values of
K, Q, a n d N that are d e t e r m i n e d in this m a n n e r will
vary considerably at times from their true values as
defined in the basic assumptions.
There are a n u m b e r of methods that can be used
to d e t e r m i n e the n u m e r i c a l values of Es, K, Q, N, A,
and B in Eq. [9] from e x p e r i m e n t a l discharge data,
most of which are unsuitable. The least squares so-
lution is p a r t i c u l a r l y involved and time-consuming.
The following approach is easily applied, rapid, rea-
sonably accurate and is used in fitting Eq. [9] to dis-
charge curves obtained at a n u m b e r of c u r r e n t den-
sities. I n Fig. 1, four points, labeled 1, 2, 3, and 4
have b e e n selected on two discharge curves which
were obtained at the m o d e r a t e l y low c u r r e n t density,
ia, and the moderately high c u r r e n t density, ib. The
values of E and (it) at points 1, 2, 3, and 4 are El, E2,
E3, and E4 and i b t l , iat2, ibt3, and iat4, respectively.
These four points are chosen to the right of the initial
potential drop. Thus the value of A e x p ( - - B Q - l i t ) is
negligible and the potential at point 2 is found from
Eq. [9] to be a p p r o x i m a t e l y
Ee = Es -- K ( Q ~Q iat2 ) i a - - N i a [10]
Similarly
O
E4 = Es-- K (. Q ~iat4 ) ia -- Nia [11]
Subtracting Eq. [11] from Eq. [10] gives
( Q ( i a t ~ - i~t~) 1112]
E2 -- E4 ~ Kia ( Q -- iat4) ( Q iat2)
- -
The equation for E1 -- E.~ is obtained in a similar m a n -
ner and is divided into Eq. [12] to give
E2 ~ E4 ia (iat4 - - iat2) (Q - ibt~) (Q -- i~tl)
[13]
[8] E1--E3 ib (ibt~--istl) (Q--iat4)(Q--iat~)
W h e n n u m e r i c a l values of E, i, and (it) are t a k e n
from the discharge data in Fig. 1 and substituted in
Eq. [13], a quadratic equation i n Q is obtained which
is solved to give a n u m e r i c a l value of Q. This value
of Q is substituted in Eq. [12] and solved to obtain a
n u m e r i c a l value of K. W h e n these values of Q and K
are substituted in Eq. [10] and a similar equation for
El, two simultaneous equations are obtained which
may be solved to give n u m e r i c a l values for Es and N.
When these values of Es, N, K, and Q are substituted in
Eq. [9], E is obtained as a specific function of (it).
The calculation of Q by use of Eq. [i3] can generally
be simplified by choosing point 2 in a m a n n e r such that
iat2 equals either ibt3 or ibtl.
The two discharge curves, ia and io, that are chosen
as a basis for these calculations should be r e p r e s e n t a -
tive of the complete set of discharge curves and should
[9] show no obvious visual discrepancies that would in-
dicate variations not p r e s e n t i n the other curves. They
are selected in the following m a n n e r . If (it) is held
constant, Eq. [9] shows that the potential E to the
right of point b in Fig. 1 m a y be stated as a linear
function of the c u r r e n t density, i, in the form
E = Es -- Bli [14]
where B1 is a constant equal to K ( Q -Q- i t ) 27N
A fairly good fit to Eq. [14] is shown in Fig. 2 where
E has been plotted as a function of i for five values of
 Vol. 112, No. 7 DESIGN OF P R I M A R Y A N D S E C O N D A R Y CELLS 659
2.5 Table I. Values of AE in volts

2.4
(it)
i 2 5 10 20 30 50 65
2,5
2 0,116 0,106 0,091 0.068 0.045 0.019 0,007
i0 0,133 0.118 0.088 0,057 0.037 0.013 0.002
20 0.145 0.123 0.0S7 0,050 0.032 0.008 0.000
2.2 40 0.144 0.120 0.084 0,048 0,027 0.006 0.000
60 0.141 0.117 0.087 0,056 0,030 0.008 0.002
80 0.140 0.115 0,096 0,056 0.031 0.003 0,001
g~ 100 0,143 0.123 0,085 0,049 0,026 0.009 0.003
120 0.153 0.118 0.085 0,049 0.025 0.010 0.000
m

2s Avg. 0.139 0.118 0.087 0.054 0.032 0.0095 0.0018

g r e a t e r than it is for p o i n t f. Th e v a l u e of E for point

15 \ 4 is a p p r o x i m a t e l y 0.02v g r eat er t h a n it is for point e.
\ Po i n t 1 is chosen s o ibtl equals a p p r o x i m a t e l y 0.5 ibt3.
\ If ibtf/iate is less t h a n 0.7, point 2 is chosen directly
\ above point 3 so t h a t iat2 w i l l e q u a l ibt3. If ibtf/iate
\ is g r e a t e r t h a n 0.7, point 2 is chosen directly above
1.7--
l_ l .A
0.1 02
i (AMP/CM z )
Fig. 2. Potential during cell discharge vs. current density for
constant values of (it). The it values in amp-hr/cm2: O, 0.00266;
~], 0.00532; A , 0.00798; e, 0.01063; II, 0.01329.
(it) using the discharge data for the l e a d - z i n c cell
shown in Fig. 4g. T h e potentials, E at the c u r r e n t
density, i = 0.0798 a m p / c m 2, w e r e considerably l o w e r
than t h e straight lines d r a w n t h r o u g h th e c o r r e s p o n d -
ing values of (it), thus showing that this p a r t i c u l a r dis-
charge was out of a g r e e m e n t w i t h the r e m a i n d e r of
the data. Variations this l a r g e w e r e not o b s e r v e d as
a rule. Th e r e m a i n i n g four values of i g a v e good
straight line fits in Fig. 2. Either of the two l o w values
of i could be used for ia and either of the t wo high
values could be used for ib. As a rule a plot of E vs. i
for each of two values of (it) w i l l be sufficient to se-
lect satisfactory values of ia and lb. Points such as A
which w e r e t a k e n past the k n e e of the discharge c u r v e
should not be used in m a k i n g up these charts of E v s i.
V e r y l o w v a l u e s and v e r y high values of i are av o i d ed
if feasible in selecting ia and ib since these e x t r e m e
values h a v e a t e n d e n c y to be less accurate. With a
little experience, ia and ib often can be selected on the
basis of j u d g m e n t w i t h o u t d r a w i n g up a c h a r t such
as that shown in Fig. 2.
If Eq. [9] is a p e r f e c t fit for the discharge data, then
the plot of E vs. i as il lu s tr a te d in Fig. 2 w o u l d con-
sist of straight lines intersecting on the E axis at E
Es. If the plot of E vs. i gives lines that do not intersect
on the E axis or if they are curves, then Eq. [9] does
not describe the discharge data perfectly. H o w e v e r ,
Eq. [9] is so adaptable that it can describe such cases
with good accuracy and it has not been necessary to r e -
ject any data on this account. Discharge data w e r e n o t
accepted for study here w h e n e v e r they w e r e so erratic
and full of e r r o r that a plot of E vs. i did not give
some s em b l an ce of a smooth curve. It was found that
all of the data that w e r e acceptable on this basis could
be fitted by Eq. [9]. V i r t u a l l y all of t h e r o o m t e m -
p e r a t u r e discharge data t a k e n f r o m the l i t e r a t u r e w e r e
found to be acceptable. At lo w t e m p e r a t u r e s the a v a i l -
able data w e r e m o r e erratic and less acceptable.
The points 1, 2, 3, and 4 used to calculate the n u -
me ri cal v a l u e s of the p a r a m e t e r s K, Q, and N are se-
lected in t h e m a n n e r il lu s tr a te d in Fig. 1. A t a n g e n t is
d r a w n to the high c u r r e n t density discharge c u r v e at
point d and point f is selected to be 0.1v b e l o w t h e
tangent line. P o i n t d is d e t e r m i n e d by eye by laying
a t r a n s p a r e n t plastic straight edge t a n g e n t to the
c u r v e and ad j u s t in g the point of t a n g e n c y u n t i l ibt~
equals 0.5 ibtf. This m e t h o d is rapid and sufficiently ac-
curate. P o i n t e is located in a m a n n e r s im i lar to f.
Th e v a l u e of E for point 3 is a p p r o x i m a t e l y 0.03v
point 1 so that iat~ wilI e q u a l ibtl. This p r o c e d u r e gives
an a p p r o x i m a t e location of the points w h i c h supply t he
n u m e r i c a l data to substitute in Eq. [12] an 4 [13], and
m a k e possible the calculation of n u m e r i c a l values of
K, Q, N, and Es w h i c h can be substituted in Eq. [9]
along w i t h values of A and B to give a f a i r l y good n u -
m e r i c a l description of the discharge data. Values of E
vs. (it) for different discharge rates can be calculated
f r o m this n u m e r i c a l e q u a t i o n and c o m p a r e d to the
actual discharge data. If t h e a g r e e m e n t is not good
enough, it can be i m p r o v e d by t h e m e t h o d of successive
approximations. A n e w calculation can be m a d e using
slightly different locations for one or m o r e of the
four points on t h e t w o discharge curves, ia and lb. If
the calculated points w e r e too far a w a y f r o m t he
m e a s u r e d results in the area to the left of some point
such as 4, it could be co r r ect ed by selecting a n e w
location for point 4 w h i c h w o u l d be slightly to the left
of the old location and calculating a n e w n u m e r i c a l
equation. T h e points calculated by this n ew equation
to the r i g h t of point 4 w o u l d be a little f a r t h e r a w a y
f r o m the actual discharge data as a r o u g h r u l e t h a n
those calculated from t h e first equation. A f a i r l y good
fit should be obtained w i t h the first calculated e q u a -
tion. If it is at all possible, a v e r y good fit w i l l h a v e
been obtained by t h e t h i r d calculation. E a c h calcula-
tion should take less t h a n one hour of time.
The calculations thus f ar are sufficient to give a
n u m e r i c a l e v a l u a t i o n of Eq. [8], w h i c h is p l o t t e d in
Fig. 1 as a dotted line f r o m a to b and a solid line f r o m
b to c. Th e difference in potential, AE, b e t w e e n this
calculated dotted l i n e of Eq. [9] and the t r u e dis-
charge potential sh o w n b y t h e solid line gb in Fig. 1
is a p p r o x i m a t e d by t h e t e r m A e x p ( - - B Q - l i t ) in Eq.
[10]. In Tab l e I values of AN vs. it are g i v en for each
discharge c u r v e of t h e Edison cell sh o w n in Fig. 4a.
The a v e r a g e values of AE Vs. (it) in Table I are plotted
on semi log p ap er in Fig. 3 and fitted by a straight line
0100
g
>o
w
<1
O.OlO
O.OOI __ [ ~ I l__l _l [
]0 20 50 40 50 60 70 80
it (AMPERE HOURS/CELL)
Fig. 3. Determination of AE from numerical data

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 660 JOURNAL OF THE ELECTROCHEMICAL SOCIETY J u l y 1965

~176 ~ ~ i o it
~To ~Io ,lo Jo ~io ,;~ ,I,o ,~o
(AMPERE HOURS/CELL)

Fig. 4a-g. Comparison of points calculated from discharge

~-o ,~o 21o Jo !o it
Jo ~o !o
( AMPERE HOURS/CELL)
!o Jo ,oo
equations with solid lines representing actual discharges at various Fig, 4c. Silver cadmium cell, AgO-Cd-KOH. Calculated points,
current densities, a. Edison cell, NiOOH-Fe-KOH. Calculated points, amp/cell: O, 0.625; e, 2.5; A, 10.0; A, 40.0.
amp/cell: O, 2; e, 10; ~ , 20; ~ , 40; A, 60; v , 80; ~ , 100;
Ig, 120. 2.S

2.0

i ~
1.5 ",

o
~
>

ua

zo 3o 40 50 50
it(AMpERE HOURS/CELL1

Fig. 4d. Lead acid cell, PbO2-Pb-H2SO~. Calculated points,

l.O
amp/ceil: O, 0.8; A, 2; El, 4; ~ , 8; e, 10; A, 20; II, 40; , , 60;
ii
50
(AMPERE HOURS/CELL)
(00 + , 80.

Fig. 4b. Silver cell, AgO-Zn-KOH. Calculated points, amp/cell:

e ~ O , 2.5; A - A , 10; II1-[~, 60.

w h o s e e q u a t i o n is ~E = A e x p ( - - B Q - l i t ) . T h e i n t e r -
c e p t o n t h e o r d i n a t e g i v e s t h e n u m e r i c a l v a l u e of A.
T h e n u m e r i c a l v a l u e of B / Q c a n b e c a l c u l a t e d f r o m
the slope or from a single point taken on the straight ~ i ~ , , i ~'"~ ' " % , "', o . ..
line. I n n e a r l y all cells t h e v a l u e of h E is m u c h less a t
h i g h v a l u e s of it/Q t h a n i n t h e e x a m p l e s h o w n i n Fig. 0.5

3 w h e r e ~ E = 0.006v a t ~ t e q u a l s 50 o r it/Q e q u a l s
0.433. I n m o s t c e l l s ~ E w o u l d b e less t h a n 0.006v a t a 1 • ...... l ..... L. . . . L__
v a l u e of it/Q e q u a l to 0.10 a n d w o u l d b e close to z e r o 5 10
it (AMPERE
15
HOURS~CELL~
20 Z~ 30

i n v a l u e a t it/Q e q u a l s 0.15. I f p o i n t s 1 a n d 2 w e r e
c h o s e n i n Fig. 4a a t it = 50 t h e n a c o r r e c t i o n of ~ E
0.006v s h o u l d b e s u b t r a c t e d f r o m t h e v a l u e s of E1 a n d
E 2 to b e u s e d i n c a l c u l a t i n g t h e c o n s t a n t s i n Eq. [9].
T h i s v a l u e of a E c o u l d n o t b e e s t i m a t e d a c c u r a t e l y
u n t i l a f t e r t h e first c a l c u l a t i o n h a d b e e n m a d e .
Discussion of the Equation and its Applications
E x p e r i m e n t a l d i s c h a r g e d a t a f o r a n u m b e r of d i f -
f e r e n t t y p e s of b a t t e r i e s h a v e b e e n p l o t t e d as s o l i d
l i n e s i n Fig. 4 (1, 2, 3, 4, 5). T h e p o t e n t i a l E is s h o w n
f o r v a r i o u s c u r r e n t d e n s i t i e s , i, as a f u n c t i o n of (it)
w h i c h is e x p r e s s e d i n a m p e r e h o u r s p e r s q u a r e c e n t i -
Fig. 4e. Dry cell. Calculated points, amp/cell: V, 0.125; O, 0.25;
o, 0.5; ~ , 1.0; A, 2.0; [~, 3.0; X, 4.0; II, 6.0; -t-, 8.0.
m e t e r or a m p e r e h o u r s p e r cell w h e r e t h e a r e a is n o t
k n o w n . E q u a t i o n [9] h a s b e e n fitted n u m e r i c a l l y to
e a c h s e t of d i s c h a r g e d a t a t h u s o b t a i n i n g a d i f f e r e n t
n u m e r i c a l e q u a t i o n f o r e a c h c h a r t i n Fig. 4. T h e n u -
m e r i c a l v a l u e s of t h e c o n s t a n t s f o r e a c h of t h e s e e q u a -
t i o n s a r e s h o w n i n T a b l e II a n d a r e d e p e n d e n t o n t h e
u n i t of t i m e , t, a n d also o n t h e u n i t of a r e a u s e d i n
d e f i n i n g t h e c u r r e n t d e n s i t y . S i n c e t h e a r e a is u n -
k n o w n i n m o s t cases, t h e a r e a of t h e e n t i r e cell is

Table I1. Values of the parameters in Eq. [9] for various types of cells

B/Q
T y p e cell Fig. No. E~, v K, o h m cell* Q, a m p - h r / c e l l * N, o h m cell* A, v Cell* ( a m p - h r ) -1 T e m p , ~ Ref.

Edison 4a 1.3080 0.0003936 115.4 020390 0.165 0.06564 Room 1

Silver-zinc 4bl 1.8310 0.005138 37.06 -- 0.00388 0.020 0.60 27 2
4b2 1.5567 0.00040 112.0 0.00067 27 2
Silver-cadmium 4cl 1.3733 0.00831 28.68 --0.00543 27
4c~ 1.0990 0.00260 95.75 -- 0.000965 27
Lead acid 4d 2.0030 0 2189 58.31 -- 0.0150 25 3
D r y cell 4e 1.2743 0.3343 25.61 -- 0.269 0.360 2.197 25
Ni-Cd 4f 1,2021 0.001358 74.67 -- 0.000241 0.080 0,1386 -- 18 4
Lead-zinc 4g* 2.4607 0.9722 0.01737 0.3589 27 5

* T h e w o r d cell i s d e f i n e d as t h e e l e c t r o d e a r e a of t h e e n t i r e cell. I t is r e p l a c e d i n 4g b y c m ~. S i n c e t h e a r e a t e r m s c a n c e l o u t i n Eq. [9],

i t is n o t n e c e s s a r y to k n o w t h e n u m e r i c a l v a l u e of t h e a r e a .

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 Vol. 112, No. 7 DESIGN OF PRIMARY AND SECONDARY CELLS
I 20 - - 30 40 50
il (AMPERE HOURS/CELL)
Fig. 4I:. $intered nickel cadmi,.m cell, NIOOH-Cd-KOH, --IS~
Calculated points, amp/celh 9 151 ~ , 241 ~ , 651 e, 1201 A , 2001
n, 300.
~,-~,,~ ~" '
\\
0002 0004 OOO6 0008 O01 OO1~ OOI4
ii IAMPERE HOURS/CM 2 )
Fig. 4g. PbO,~-Z.-H2SO,~ reserve cell. Calculated paints, amp/cm2:
9 0.00957; o, 0.03191 A, 0.0798; II, 0.15951 I-I, 0.2393.
t a k en as the unit area and the c u r r e n t density is de-
fined as the amperes per cell and is e q u a l in v a l u e to
the total discharge current. T h e points in Fig. 4 are
calculated from these equations. It can be seen that
the calculated points give good fits in e v e r y case to
the solid lines that r e p r e s e n t the actual discharge data.
Thus the i n f o r m a t i o n in Table II is sufficient to give
an excellent description of the discharge data in Fig.
4 at a considerable savings in space. E q u a t i o n [9] was
applied to a w i d e v a r i e t y of discharge data f r o m v a r i -
ous types of physically constructed batteries for each
of the common b a t t e r y systems. The e x a m p l e s selected
for Fig. 4 w e r e in each case the one w h i c h covered the
widest ran g e of c u r r e n t densities. E q u a t i o n [9] was
also fitted successfully to discharge data f r o m t h e fol-
lowing systems: PbO2-Cd-H2SOR, H g O - I n - K O H , air
c e l l - a i r - Z n - K O H , AgCI-Zn-NaC1, PbO2-Pb-HC10~,
C u O - Z n - N a O H , N i O O H - Z n - K O H , Clz-Zn-ZnCI~, PbO~-
Sn-HC1OR, PbO2-Pb-HBFR, H g O - Z n - K O H . No indi-
v i d u a l curves w e r e o m it te d in any case. The poorest fit
obtained in all the cases studied was w i t h the d r y cell
data which is shown in Fig. 4e. Most of the data was
t a k e n from t h e l i t e r a t u r e and was selected to c o v er as
wide a range of c u r r e n t densities as possible. U n -
fortunately, the amount of low t e m p e r a t u r e discharge
data was limited and some of it had to be r e j e c t e d as
erratic w h e n tested by the m e t h o d illustrated in Fig. 3.
In Fig. 4b and 4c the discharge took place in t w o
steps and it was found that a separate equation could
be fit to each step. The first step in each case is indi-
cated by the subscript 1 on the figure n u m b e r in
Table II. F o r example, the e q u a t i o n for the silver cell
in Fig. 4b wo u l d be
E ~ 1.8310 - - 0.005138
37.06-- i t i q-
0.00388 i + 0.020 e x p (--0.60 it)
or
112 - - it
w h i c h e v e r is h i g h e r in value.
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661
W h e n e v e r the calculated values of Es, K, Q, and N
are the t r u e or defined values and are not affected by
t h e choice of the f o u r points, Eq. [9] fits that p a r t i c u -
lar discharge data theoretically. W h e n e v e r the calcu-
lated values of Es, K, Q and N are not the true or de-
fined values and are affected by t h e choice of points
1 to 4, Eq. [9] is fitting that p a r t i c u l a r discharge data
empirically. I n this l a t t e r case, t h e r e are a n u m b e r of
specific combinations of n u m e r i c a l v a l u e s of Es, K, Q
and N w h i c h w i l l give good fits to a p a r t i c u l a r set of
discharge curves. A m o n g these combinations Es and Q
w i l l be f a i r l y constant w h i l e K and N m a y v a r y some-
what, N becoming smaller as K becomes larger. F or
example, t w o individuals fitting Eq. [9] to a p a r t i c u l a r
60 70
set of discharge curves m i g h t get t w o different e q u a -
tions, each of w h i c h fit the data quite w e l l e v e n though
they h ad appreciably different values for K and N.
As a v e r y r o u g h rule, a closer approach to a t h e -
oretical fit is g en er al l y found in t h e presence of one
or m o r e of the f o l l o w i n g conditions: the discharge data
covers a n a r r o w r an g e of c u r r e n t densities, the p o t e n -
tial d r o p due to polarization is low, t h e electrolyte
does not change in composition d u r i n g discharge, the
slope of the discharge curves before the knee is r e l a -
t i v e l y small, t h e ratio (it)/Q is f a i r l y l a r g e and covers
a r e l a t i v e l y n a r r o w r an g e of values of (it), and the
calculated v a l u e of N is not negative. Most of these
conditions can be observed in Fig. 4a.
I n any case, Eq. [9] is so adaptable that w i d e v a r i -
ations in its constants, p a r t i c u l a r l y K and N, enable it
to be fitted w i t h good accuracy to a v e r y w i d e r a n g e
OOI6 OOIB OOE
of discharge data. A l ar g e increase in the n u m e r i c a l
v a l u e of K w i l l be accompanied by such a l ar g e de -
crease in t h e v a l u e of N that N w i l l often be n e g a t i v e
in v a l u e as can be seen in Table II. Since N is the in-
t e r n a l resistance in the original d e r i v a t i o n and t h e e -
r et i cal l y cannot be n e g a t i v e in value, it is obvious
t h a t Eq. [9] m u s t be considered to be e m p i r i c a l in most
of its c u r v e fitting applications and t h e r e is no reason
to b e l i e v e that it should h a v e to describe f u l l y the dis-
c h a r g e of e v e r y t y p e of battery.
In Fig. 2 the m e a s u r e d potential is low for the points
at i equals 0.0798 a m p / c m 2. In Fig. 4g the m e a s u r e d po-
tential at this c u r r e n t density is ap p r eci ab l y l ow e r
than the calculated p o t en t i al thus indicating the v e r y
strong likelihood of an er r o r in this data. W h e n t he r e
are only t h r e e discharge curves and t w o of t h e m are
correct, it is not possible to tell by this m e t h o d w h i c h
one of the t h r e e is in er r o r w i t h o u t collecting m o r e
data. A f o u r t h discharge m a d e at a different c u r r e n t
density will, if correct, d e t e r m i n e w h i c h of the other
t h r e e curves contains the error.
An e x a m i n a t i o n of all of t h e data fitted by Eq. [9]
shows t h a t t h e differences b e t w e e n t h e calculated and
t h e m e a s u r e d results are often l a r g e r at the hi ghe s t
c u r r e n t densities t h a n t h e y are at i n t e r m e d i a t e c u r r e n t
densities. This l a r g e r v a r i a t i o n can be a t t r i b u t e d to
the high r e l a t i v e dispersion of the data; the fact that
the h i g h l y simplified calculation methods g i v en here
t e n d to give t h e poorest fit at high c u r r e n t densities;
and the fact that the poorest fit is often obtained at the
e x t r e m e limits w h e n fitting equations to m e a s u r e d data.
T h e r e is also a t e n d e n c y for a v e r y f e w of the calcu-
lated curves at the lowest c u r r e n t density to h a v e less
slope and a sm al l er capacity t h a n the observed data.
This condition is most noticeable in Fig. 4g and seems
to be most g e n e r a l l y associated w i t h batteries whose
electrolytes change ap p r eci ab l y in concentration d u r -
ing discharge. As a r o u g h em p i r i cal approximation, it
is assumed that the drop in potential in a b a t t e r y is
d i r e c t l y p r o p o r t i o n a l to the change in el ect r o l y te con-
centration during discharge, assuming all other factors
are neglected. E q u a t i o n (9) can t h e n be w r i t t e n as
E=Es-- ~ ~--Niq-Aexp(--BQ-lit)--Cit
[15]
w h e r e C is a constant.
 662 JOURNAL OF THE ELECTROCHEMICAL SOCIETY July 1965
2.5

6 B i

~EO
i 1 "\

'50 oooz 0004 ~ I 6 _ I 0O08 I I I I

I 9 . O.OtO
it (AMPERE HOURSlCM~(
0.012 0.014 ~ 0016 00~8 002

I Fig. 6. Comparison of points calculated from the discharge equa-

I tion with solid lines representing actual discharges at various
I current densities. PbOE-Zn-H2S04 reserve cell. Calculated points,
t5 i b t7
amp/cm2: O, 0.00957; o, 0.0319; ~ , 0.0798; El, 0.1595; [~, 0.2393.
9 =

lot6 i018 it

Fig. 5. Typical discharge curves to be used in numerical calcula- 1.7

tion of C.

To d e t e r m i n e the n u m e r i c a l v a l u e of C select four

L5
points as shown in Fig. 5 which are far enough past to
the initial potential drop for the e x p o n e n t i a l term to
be negligible. F r o m Eq. [15] L4

(
E~ -~ Es -- Kib \ Q Q ibt~ ) -- Nib - - Cibt5 [16]
L3

12 I f f I I I i t i l
and 0 I 2 3 4 5 6 u 8 9 LO [I
Q i t (AMPERE-HOURSPER CELL)

ET~-Es--Kib ( Q~ibt;)--Nib--Cibt7 [17]

Fig. 7. Comparison of the charge data of a Ni-Cd cell with
the calculated results for various current densities. Nickel cadmium
S u b t r a c t i n g Eq. [17] from Eq. [16] gives cell, Ni-OOH-Cd-KOH. Calculated points, amp/cell: O, 16.0; A ,
2,5; e, 0.16.
)] Equation [21] can be obtained from Eq. [9] by r e -
versing the signs of the last three terms. Equation [21]
+ C(ibt7 - - ibts) [18]
has been fitted to the charge of a N i - C d cell i n Fig. 7.
Similarly The solid lines represent the actual data and the points
Q are calculated from the equation

From Eq. [18] and Eq. [19]
ib (E6 - - Es)
C=
(ib -- ia) (ibt7 -- ibt5)
Numerical values of C are calculated from Eq. [20]
and substituted in Eq. [15].
Let E' = E A- Cir.
E = 1"379 + 0"0024 ( 1 )
+ C(ibt~--ibts) [19] 1 -- 0.095 it
i --0.00116 i - - 0.08 exp (.--0.693 it)
- - ia (E5 - - E~) The use of Eq. [21] in describing the charging of a
[20] cell has b e e n tested on a very limited a m o u n t of data.
Consequently, it is not yet certain to what extent it
can be successfully applied.
The total energy Wt that has been evolved from the
b e g i n n i n g of the discharge u p to time t is defined by
the e q u a t i o n

T h e n El" = E1 -~ Ci~tl, E2' ~- E2 -J7 Ciat2, E3" ~- E3

+ Cibt3, and E4" = E4 ~- Ciat4. If El', E2", E3", a n d E~'
are substituted for El, E2, E3, E4, respectively, i n Eq. S u b s t i t u t i n g Eq. [8]
Wt =
Jo' i E dt

[10] to [13], they can be used to calculate n u m e r i c a l Q

values of Q, K, N, and Es in the m a n n e r previously
described. -1
Numerical values of Eq. [15] were d e t e r m i n e d i n is -- Ni ~ ~- A i exp ( - - B Q - l i t ) I dt
this m a n n e r for the lead-zinc cell shown in Fig. 4g [22]
a n d f o u n d to be W t = [Esit -b K Q i l n (Q - - i t ) -- Niet
A Q / B e x p ( - - B Q - l i t ) ]to [23]
E = 2.4775 -- 0.9237 ( 0 0" .001T8~1 )~i _ it
0.4295i_4.25it - -

W t =E~it -- K Q i In (1 -- i t / Q ) -1 _ Ni2t
Calculated points from this equation are shown i n A- A Q / B ( 1 - - exp(--BQ-lit)) [24]
Fig. 6 to give a better fit to the e x p e r i m e n t a l data
t h a n was obtained by the use of Eq. [9]. The constants from an equation describing the dis-
If the basic assumptions are assumed to be true d u r - charge of a Ni-Cd cell at 27~ were substituted i n Eq.
ing the charge of a cell, then the following equation [24] a n d the total energy evolved at t i m e t was found
would hold for the potential d u r i n g charge to b e
W t = 1.25 i t - - 0.0238 i In (1 -- 1.05 it) -1
E=EsA-K ~ "A-Ni--Aexp(--BQ-lit) [21]
--0.006i 2t A- 0.0248 [ 1 - - e x p ( - - 3 . 8 3 i t ) ] [25]

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 Vol. 112, No. 7 DESIGN OF PRIMARY AND SECONDARY CELLS 663

,~ i.o
o

~o~
0.5

%o,
//'/// Ol
I
IO
I
IO ioo
2

t {HOURS)

Fig. 8. Comparison of the energy evolved during the discharge I I I

20 40 60
of a Ni-Cd cell with the calculated results for various current CURRENT DENSITY, L (AMP/CELL)
densities. Sealed nickel cadmium cell, NiOOH-Cd-KOH, 27~
Calculated points, amp/cell: o, 4.5; 9 0.56; 17, 0.14; A , 0.035; Fig. 10. Es-Ni-Ki plotted as a function of current density
A , 0.010.
2O

2C

o
>1

J l I I
2 3 4 5 6

Q--it

Fig. 9. Discharge curves showing the potential as a function of 060

I
OI
L
02
I
03
I
04
I
05
I
06
I
07
I
0.8
I
09 I0
Q/Q-it for various current densities. Lead acid cell, PbO2-Pb-H2S04. It/Q
Current density, amp/celh O, 0.8; A , 2; [~, 4; V , 8; e, 10;
A , 20; I , 40; ~,, 60; -f-, 80. Fig. 11. Discharge curves showing the cell potential during dis-
charge as a function of the fraction of active material used up at
any given time.
In Fig. 8, Wt in w a t t hours p e r cell for a N i - C d b a t -
t e r y has b e e n plotted as a f u n c t i o n of t in hours for Rate Q/i
various values of the cell c u r r e n t in amperes. The solid A, Lead acid 11 hr 14.6 hr
lines are obtained from calculations based on n u m e r i c a l A1, Lead acid 1 hr 2.8 hr
i nteg r at i o n of the actual discharge data. The points are B, Silverzinc 11 hr 11.2 hr
calculated f r o m Eq. [24]. T h e a g r e e m e n t b e t w e e n the El, Silver zinc I hr 1.14 hr
calculated and the m e a s u r e d results in such cases d e- C, Edison 11 hr 11.3 hr
pends e n t i r e l y upon h o w w e l l Eq. [9] can be fitted to C1, Edison 1 hr 1.12 hr
the original discharge data. D, Dry cell 11 hr 25.6 hr
Once the discharge is past the initial potential drop, D1, Dry cell 1 hr 6.4 hr
the e x p o n e n t i a l t e r m becomes negligible and Eq. [9]
can be w r i t t e n as m e t h o d of Fig. 9 and 10 can be used in fitting Eq. [9]
to discharge data w h e n e v e r t h e v a l u e of Q is known.
E = Es-- N i - - ~ Ki [26"1 If the basic assumption holds true, then Q can be cal-
culated f r o m the a m o u n t of active m a t e r i a l cn the con-
which shows the p o t e n ti a l E to be a l i n e a r function trolling electrode and the graphical m e t h o d is a p-
of Q / ( Q - - i t ) w i t h slope - - K i for any g i v e n c u r r e n t plicable. In the m o r e empirical applications, such as
density, i. A c t u a l discharge potentials w e r e t a k e n the lead acid b a t t e r y j u s t shown, the calculated v a l u e
f r o m the lead acid b a t t e r y discharge data in Fig. 4d of Q w i l l be s o m e w h a t less than t h e v a l u e d e t e r m i n e d
and plotted in Fig. 9 against Q / ( Q - - i t ) f o r each of f r o m the a m o u n t of active m a t e r i a l and t h e graphical
nine cu r r en t densities. S t r a i g h t lines gave good fits to m e t h o d w o u l d not be accurate. A l m o s t all of t h e a v a i l -
these plotted points. The a v e r a g e v a l u e of the K's, d e- able discharge data gave no i n f o r m a t i o n on the a m o u n t
t e r m i n e d f r o m the slopes of each of these nine lines of active m at er i al s and c o n s e q u e n t l y the feasibility of
was 0.0195 as c o m p a r e d to th e calculated v a l u e of using this graphical m e t h o d for fitting Eq. [9] to dis-
0.0189 g i v en in Table II. charge data has not y et been d et er m i n ed .
In Fig. 9 the values of E for Q / ( Q -- it) equals one
can be seen f r o m Eq. [2,6] to be Presentation of Discharge D a t a
E = E s - - (N Jr K ) i [27] A study of Eq. [9] suggests the possibility of pl ot -
ting b a t t e r y discharge data against dimensionless q u a n -
w h i ch shows E here to be a linear function of i w i t h tities in a m a n n e r that w o u l d m a k e possible m o r e
slope, - - ( N + K) , and intercept, Es. Values of E for direct comparisons b e t w e e n v a r i o u s types of cells. In
Q / ( Q -- it) equals one w e r e ta k e n f r o m Fig. 9 and Fig. 11 t h e potential d u r i n g discharge is p l o t t ed as a
plotted in Fig. 10 to give a straight line. T h e n u m e r i c a l function of it/Q w h e r e it/Q is t h e f r a c t i o n of active
values of Es and N d e t e r m i n e d f r o m this straight line m a t e r i a l used up at time, t. Discharge data are shown
w e r e 1.998 and --0.0155 as c o m p a r e d to t h e calculated h e r e at the 1-hr and t h e l l - h r r a t e for four c o m m o n
values of 2.003 and --0.0150 g iv e n in T a b l e II. Th e types of cells. The v a l u e of it/Q at the end of the dis-
values of Es, K, and N d e t e r m i n e d by th e t w o methods charge is t h e efficiency of utilization of the active
are v i r t u a l l y identical and show that the graphical material. In each case, the discharge was assumed

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 664 JOURNAL OF THE ELECTROCHEMICAL
to be ended w h e n ~ equalled Es -- K i -- N i -- 0.25v.
Thus in Fig. 1, curve ia, the end voltage would be
0.25v below the voltage at point a. A drop of more
t h a n 0.25v would have precluded the use of much
of the available data. I n Fig. 4 the discharge curves
are shown as dotted lines w h e r e v e r they extended
past this assumed end point.
Here i n Fig. 11 is a method of comparing at equal
discharge times such factors as efficiencies, potentials,
variations of potentials with time, potential drops due
to i n t e r n a l resistance, etc., for various types of con-
structions of ceils. The two curves at A1 represent
two different sizes and constructions of lead acid cells.
Although the difference i n discharge characteristics is
small b e t w e e n these two cells, it could, i n m a n y cases,
be quite large and could be readily d e m o n s t r a t e d on
a chart of this type. Other things being equal, the cell
size is not i m p o r t a n t here, since each cell is being
discharged at a p a r t i c u l a r value of Q / i that is held
constant w i t h change i n cell size, which is e q u i v a l e n t
to saying n times the c u r r e n t would be d r a w n from a
cell n times as large. The values of Q / i given i n Fig.
11 r e p r e s e n t the time each cell would have taken to
discharge 100% of the active m a t e r i a l on the control-
ling electrode at the particular c u r r e n t density, i. The
discharge characteristics of the four cells in Fig. 11
could have been compared by plotting E vs. i t / Q at a
constant v a l u e of Q / i such as 10 hr, thus giving a
slightly different graph. A n u m b e r of other variations
can be made of this chart. The vertical axis could be
the ratio of the discharge potential to the theoretical
potential. I n this case the area u n d e r the curve would
be the theoretical watt hour efficiency. If the vertical
axis were the ratio of the discharge potential to the
average charge voltage, Ec, the area u n d e r the curve
would be the watt hour efficiency defined by the ratio
of the output in watt hours to the i n p u t in w a t t hours.
The equation for this latter curve can be obtained by
dividing Ec into Eq. [9] to give
K 1 ] K
(E~.) ~ (-~-c)--('~ i)[ 1--(it~Q)
where each q u a n t i t y in brackets or parentheses is di-
mensionless. I n Fig. 11 the values of i t / Q were t a k e n
from Table II and are empirical to a certain extent. If
Q had been calculated from the actual a m o u n t s of
active m a t e r i a l on the controlling electrode, its value
would have been slightly larger and the discharge
curves in Fig. 11 would be changed slightly. Values of
(it) per u n i t weight of active m a t e r i a l or per unit cell
weight, or watt hour efficiencies could have been used
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SOCIETY J u l y 1965
in place of i t / Q for the abscissa i n Fig. 11. The im-
portrait t h i n g i n each of these cases is that the use of
some form of dimensionless quantity, or factor closely
related thereto, as either or both of the coordinates
enables a quantitative, visual study and comparison
to be m a d e of the characteristics of certain types of
e q u i v a l e n t discharges, either for different types of cell
systems, or different constructions of the same cell
system, or both. As shown i n Eq. [28], the equation
for each of these cases can be obtained easily from
Eq. [9].
Manuscript received Feb. 4, 1965. This paper was
presented at the Boston Meeting, Sept. 16-20, 1962.
A n y discussion of this paper will appear in a Discus-
sion Section to be published i n the J u n e 1966 JOURNAL.
REFERENCES
1. C. F. Anderson, This Journal, 99, 244C (1952).
2. C. P. Wales, NRL Rpt 5167, 11 Aug. 1958.
3. E. A. Hoxie, Trans., AIEE, P a r t II Applications and
Industry, 73, 17 (1954).
4. G. B. Ellis, H. Mandel, and D. Linden, This Journal,
99, 250C (1952).
5. W. J. Schlo~ter, ibid., 99, 205C (1952).
GLOSSARY
A Numerical v a l u e of he at (it) ~ O (v)
T r a n s f e r coefficient (dimensionless)
Constant p a r a m e t e r (dimensionless)
C Constant p a r a m e t e r (volt cm 2 amp -1 sec -1)
E Cell potential d u r i n g discharge (v)
Ea Anode potential d u r i n g discharge (v)
Ec Cathode potential d u r i n g discharge (v)
Es A constant potential p a r a m e t e r (v)
~E Initial potential drop (v)
n S t e a d y - s t a t e activation overpotential (v)
F F a r a d a y (coulombs equiv. -1)
i A p p a r e n t c u r r e n t density (amp cm -2)
~am Active m a t e r i a l c u r r e n t density (amp cm -2)
io A p p a r e n t exchange c u r r e n t density (amp cm -2)
Coefficient of polarization (ohm cm 2)
Ka Coefficient of polarization for anode (ohm cm 2)
Kc Coefficient of polarization for cathode (ohm cm 2)
N I n t e r n a l resistance of cell (ohm cm 2)
Q A m o u n t of active m a t e r i a l on controlling elec-
trode as coulombs (coulombs cm -~)
Qa A m o u n t of active material on anode as coulombs
(coulombs cm -2)
Qc A m o u n t of active material on cathode as (cou-
lombs cm -2)
R Gas constant (amp volt sec deg -1 mole -z)
T T e m p e r a t u r e (deg)
t Time ( m i n or hr)
Wt Energy evolved d u r i n g cell discharge (amp volt
see cm -2)
Z N u m b e r of electrons transferred in rate deter-
m i n i n g step (dimensionless)