Vol. 124, No.

10

HIGH ION OXIDE CONDUCTION

sphere, it m a y be a v a i l a b l e for p r a c t i c a l solid electrolytes u n d e r oxidizing a t m o s p h e r e because of its high

conductivity and easy p r e p a r a t i o n .
M a n u s c r i p t s u b m i t t e d A p r i l 26, 1977; r e v i s e d m a n u script received J u n e 10, 1977.
A n y discussion of this p a p e r will a p p e a r in a Discussion ~ection to be p u b l i s h e d in the J u n e 1978 JOURNAL.
A l l discussions for the J u n e 1978 Discussion Section
should be s u b m i t t e d b y Feb. 1, 1978.

Publication costs o] this article were assisted by

the authors.
REFERENCES
1. G. G a t t o w and H. Schrhder, Z. Anorg. Allgem.
Chem., 318, 176 (1962).
2. G. G a t t o w and D. Schutze, ibid., 328, 44 (1964).
3. M. G. Hapase and V. B. Tare, Indian J. Pure Appl.
Phys., 5, 401 (1967).
4. R. S. Sethi and H. G. Gauer, Indian J. Chem., 3, 177
(1955).

1369

5. T. Takahashi, H. Iwahara, and Y. Nagai, J. Appl.

Electrochem., 2, 97 (1972).
6. T. Takahashi and H. I w a h a r a , ibid., 3, 65 (1973).
7. C. N. R. Rao, G. V. S u b b a Rao, and S. Ramdas,
J. Phys. Chem., 73, 672 (1969).
8. C. A. Johnson, R. C. Bradt, and J. H. Hoke, J. Am.
Ceram. Soc., 58, 37 (1975).
9. T. Takahashi, H. I w a h a r a , and T. Arao, J. Appl.
Electrochem., 5, 187 (1975).
10. T. Takahashi, T. Esaka, and H. I w a h a r a , ibid., 5,
197 (1975).
11. R. S. Roth and T. L. Waring, J. Res. Nat. Bur.
Stand., Sect. A, 66, 451 (1962).
12. E. M. Levin and R. S. Roth, ibid., {}8, 202 (1962).
13. C. Wagner, Z. Phys. Chem., 21, 25 (1925).
14. T. T a k a h a s h i and H. I w a h a r a , Energy Convers., 11,
105 (1971).
15. T. Takahashi, T. Esaka, and H. I w a h a r a , in J. AppL
Electrochem., 7, 303 (1977).
16. H. Yanagida, R. J. Brook, and F. A. Krhger, This
Journal, 117, 593 (1970).
17. H. Schmalzried, Z. Phys. Chem. N.F., 38, 87 (1963).

Determination of the Kinetic Parameters of Mixed-Conducting

Electrodes and Application to the System LLSb
W. Weppner and R. A. Huggins*
Department of Materials Science and Engineering, Stanford University, Stanford, California 94305
ABSTRACT
A n electrochemical galvanostatic i n t e r m i t t e n t t i t r a t i o n technique (GITT)
is described which combines both t r a n s i e n t and s t e a d y - s t a t e m e a s u r e m e n t s
to obtain kinetic p r o p e r t i e s of solid m i x e d - c o n d u c t i n g electrodes, as well as
t h e r m o d y n a m i c data. The d e r i v a t i o n of quantities such as the chemical and
component diffusion coefficients, the p a r t i a l conductivity, the mobility, the
t h e r m o d y n a m i c e n h a n c e m e n t factor, and the p a r a b o l i c rate constant as a
function of s t o i c h i o m e t r y is .presented. A description of the factors governing
t h e equilibration of composition gradients in such phases is included. The technique is a p p l i e d to the d e t e r m i n a t i o n of the kinetic p a r a m e t e r s of the compound "Li~Sb," which has a n a r r o w composition range. F o r Lie.999~Sb the
chemical diffusion coefficient is 2 10 -5 cm ~ sec -1 at 360~ This value is
quite high, due to a large t h e r m o d y n a m i c e n h a n c e m e n t factor of 1.3 104.
The l i t h i u m component diffusion coefficient is c o m p a r a t i v e l y s m a l l at this
composition, 1.5 1O-~ cm 2 sec -1. The p a r t i a l conductivity a n d electrical
m o b i l i t y of l i t h i u m are 1.5 10 -4 1%-1 cm -1 and 3 10 - s cm 2 V -1 sec - I ,
respectively, at the same s t o i c h i o m e t r y and t e m p e r a t u r e . Because of the v e r y
l a r g e values of the chemical diffusion coefficient and the fact t h a t 3 moles of
l i t h i u m can react p e r mole of antimony, this system m a y be of interest for
use in n e w types of s e c o n d a r y batteries.
Q u a n t i t a t i v e k n o w l e d g e of t r a n s p o r t kinetics in
solids is of i m p o r t a n c e both for increased u n d e r s t a n d ing of t r a n s p o r t mechanisms and the d i s o r d e r in solid
m a t e r i a l s and for the technological application of
m a n y s o l i d - s t a t e reactions. Especially in the c u r r e n t
search for n e w types of high p o w e r d e n s i t y batteries,
success in several approaches s t r o n g l y depends on the
a v a i l a b i l i t y of solid electrodes which i n c o r p o r a t e electroactive species from the e l e c t r o l y t e into t h e i r c r y s tal structures and in which the equilibration of local
differences in composition occurs rapidly.
In general, in the presence of a compositional (stoichiometric) g r a d i e n t the t r a n s p o r t p a r a m e t e r s of the
different mobile species are i n t e r r e l a t e d . The q u a n tity u s u a l l y used to describe the complex process of
compositional e q u i l i b r a t i o n ( r e l a x a t i o n ) is the c h e m ical

diffusion

coefficient, I~. Besides

the

thermo-

* Electrochemical Society Active Member,

K e y w o r d s : c h e m i c a l diffusion, g a l v a n o s t a t i c i n t e r m i t t e n t t i t r a t i o n , p a r t i a l i o n i c c o n d u c t i v i t y , t h e r m o d y n a m i c e n h a n c e m e n t fact o r , p a r a b o l i c t a r n i s h i n g r a t e c o n s t a n t , ionic mobility.

gravimetric, conductometric, and r a d i o t r a c e r methods

which have been used for a long t i m e for the o b s e r v a tion of the exchange of solid compounds with adjacent
liquid or gaseous species, electrochemical techniques
h a v e r e c e n t l y come into use (1-4). The i m p o r t a n t a d v a n t a g e of this l a t t e r a p p r o a c h is t h a t the voltage of
a suitable galvanic cell is d i r e c t l y r e l a t e d to a p p r o p r i ate t h e r m o d y n a m i c quantities, and the c u r r e n t can
p r o v i d e easily m e a s u r a b l e kinetic i n f o r m a t i o n at the
same time. F o r the case of ideal solutions and conc e n t r a t i o n - i n d e p e n d e n t diffusion coefficients, electrochemical methods have also been used in s e v e r a l
e a r l i e r investigations [e.g., (5-7)].
To s t u d y chemical diffusion in m i x e d - c o n d u c t i n g
solids one m a y e m p l o y t r a n s i e n t methods similar to
those used for the electrochemical investigation of
the kinetics in the vicinity of chemically i n e r t solid
electrodes in liquid electrolytes (chronopotentiometry,
c h r o n o a m p e r o m e t r y , v o l t a m m e t r y ) [e.g., (8)]. In the
case discussed here, however, the t r a n s p o r t in the
b u l k of the electrode acts as the r a t e - d e t e r m i n i n g step.

October 1977

J. Electrochem. Soc.: S O L I D - S T A T E S C I E N C E A N D T E C H N O L O G Y

1570

S t e a d y - s t a t e m e a s u r e m e n t s are often used to m e a sure the conductivity. However, t h e y give i n f o r m a t i o n

concerning the p r o d u c t of the concentration and the
diffusion coefficient, r a t h e r t h a n e i t h e r one separately,
without additional information. On the other hand,
t r a n s i e n t methods m a y sometimes be used to s e p a r a t e
these quantities. A n e x a m p l e is the so-called "Rosenb u r g method" for the e v a l u a t i o n of defect c o n c e n t r a tions and chemical diffusion in oxide l a y e r s (9-11).
In this paper, the application of an electrochemical
cell m e t h o d is i n t r o d u c e d for the acquisition of both
kinetic and t h e r m o d y n a m i c i n f o r m a t i o n in m i x e d conductors, such as insertion c o m p o u n d electrodes. This
m e t h o d allows s e p a r a t e d e t e r m i n a t i o n of the chemical
diffusion coefficient, as well as other useful quantities,
in one set of experiments. This a p p r o a c h employs an
e x p e r i m e n t a l l y t r a c t a b l e g a l v a n o s t a t i c i n t e r m i t t e n t ti'tration technique ( G I T T ) , which combines t r a n s i e n t
and s t e a d y - s t a t e m e a s u r e m e n t s . It eliminates the cust o m a r y p r o b l e m of i n t e r f e r e n c e due to resistance
polarization in the use of potentiostatic techniques.
The desired d a t a a r e c o n v e n i e n t l y accessible, and a
precise c o u l o m e t e r or i n d e p e n d e n t d e t e r m i n a t i o n of
coulometric t i t r a t i o n curves are not necessary.
The investigation of t r i l i t h i u m antimonide, "Li3Sb,"
b y the use of this n e w technique is d e s c r i b e d here.
Li~Sb is a m i x e d - c o n d u c t i n g compound whose f e a t u r e s
m a k e it p o t e n t i a l l y interesting for use as an electrode
constituent. A l t h o u g h the r a n g e of s t o i c h i o m e t r y of
this phase is r a t h e r narrow, so that only small stoichiom e t r i c v a r i a t i o n s m a y occur, this m e t h o d is s h o w n to
be e x t r e m e l y sensitive and quite precise.

Basic Relations
Chemical diffusion is a process in which the t r a n s p o r t of all species w i t h i n the solid is involved. G e n e r a l equations will be d e r i v e d for its microscopic
description and its r e l a t i o n to other kinetic p a r a m eters of the material. The p a r t i c l e fluxes will be e x pressed in t e r m s of the i n d i v i d u a l kinetic and t h e r m o d y n a m i c p r o p e r t i e s of the different ionic and electronic
species. This a p p r o a c h will show which factors control
chemical diffusion u n d e r various circumstances. Effects
resulting f r o m volume changes and macroscopic m o v e ments will not be considered. F o r this purpose, one
m a y often use the sublattice of one component as the
f r a m e of r e f e r e n c e for the motion of all the other
species (12). If necessary, other r e f e r e n c e systems
should be considered (13), of course. Also, it will he
assumed t h a t the diffusion l e n g t h is small c o m p a r e d
to the dimensions of the whole system.
In general, in an i s o t h e r m a l and adiabatic system
and if Onsager's cross-coefficients (12) a r e negligible,
the flux d e n s i t y of species i (in particles p e r square
c e n t i m e t e r second) u n d e r the influence of a g r a d i e n t
of the electrochemical p o t e n t i a l ~]i ( r e l a t e d to one
p a r t i c l e ) is given in the o n e - d i m e n s i o n a l case b y
j~ =

z~Yq2 Ox

[1]

r zi, and q a r e the p a r t i a l electrical c o n d u c t i v i t y due

to the t r a n s p o r t of species i, the charge n u m b e r ( v a l ence), and the e l e m e n t a r y charge, respectively. The
electrical conductivity r m a y be r e p l a c e d b y an e x pression including the p r o d u c t of the concentration ci
and the electrical m o b i l i t y ui or, a l t e r n a t i v e l y , the
g e n e r a l m o b i l i t y bi (the m e a n p a r t i c l e velocity p e r
unit general acting force), w h e r e bi : ui/lzilq

~xi: Izilqciul : ziYqYcibi

[2]

Also, the electrochemical p o t e n t i a l ~i m a y be d i v i d e d

into two terms, one containing the chemical p o t e n t i a l
gi (per p a r t i c l e ) or the activity ai, and the o t h e r the
local electrostatic p o t e n t i a l r
~li :

m + ziq~ : ~i~ + k T In a i + ziq~

[3]

~i~ k, and T are the chemical p o t e n t i a l of species i

in the s t a n d a r d state (ai = 1), Boltzmann's constant,
and the absolute t e m p e r a t u r e , respectively. Inserting
Eq. [2] and [3] into Eq. [1] yields for t h e flux d e n s i t y
of the component i

kTui[Olna, Oci
The
of a
sion
as a

ZiqCi ~b ]

[4]

factor in front of the b r a c k e t has the dimensions

diffusion coefficient and is the component diffucoefficient DKi, or the "diffusivity of the species i
component" (12)

kTui

DKi "-

[z lq

-- bikT

[5]

This q u a n t i t y is thus s i m p l y p r o p o r t i o n a l to the m o b i l i t y of the species in question and reflects the s a m e

microscopic kinetic phenomena. This diffusion coefficient obeys the N e r n s t - E i n s t e i n equation r e g a r d l e s s of
w h e t h e r the solution is ideal or nonideal, a n d is the
diffusion coefficient which is d i r e c t l y m e a s u r e d in the
case of ideal dilute solutions of n e u t r a l species. DK/
is a m e a s u r e of the r a n d o m motion of the particles
of species i in the crystal, and is r e l a t e d to the (radio)
t r a c e r diffusion coefficient DT~ b y DTI --- ]iDKi, w h e r e ]i
is the c o r r e l a t i o n factor.
The inner electric field Oq~/ax, which cannot be e x p e r i m e n t a l l y d e t e r m i n e d , m a y be e l i m i n a t e d from Eq.
[4] b y the condition that, except for t r a n s i e n t conditions i n v o l v i n g the accumulation of a significant space
charge, charge flux balance m u s t be maintained. T h a t
is, for all species, if t h e r e is no e x t e r n a l l y a p p l i e d
electric p o t e n t i a l difference
z~ji = 0

[6]

Inserting Eq. [4] into Eq. [6], and solving for Or

and then using this expression in Eq. [4] yields the
flux d e n s i t y for species i in t e r m s of t r a n s p o r t q u a n tities and activity g r a d i e n t s r e l a t e d to it and to all
o t h e r species j
3 i - - -- DKI

[
:

-- DKt

[01nai
0]nci

~
j

Oln a~

tj zi 0 1 n a i l 0ci [7a]
z--l--~
J o~z'

tj zi Olnaj] ,Sc,

( I -- it) ~ ~

Zj 0 In cl

Ox
[7b]

The summations include all other ionic and electronic

species. The s y m b o l ti -- ~i / ~
~j is the t r a n s f e r ] J
ence n u m b e r for species i.
As a result of the ionization equilibrium, in which
the activities of n e u t r a l species a r e r e l a t e d to those
of t h e i r ionic and electronic constituents w i t h i n solids,
we have
d In ai + zid In ae = d In ai -- zid In ah : d In al* [8]
w h e r e e, h, and i* r e p r e s e n t electrons, holes, and
n e u t r a l i species, respectively. E q u a t i o n [7] m a y now
be t r a n s f o r m e d into an expression containing only
the ( p h y s i c a l l y m o r e r e l e v a n t ) activities and concentrations of n e u t r a l atomic species
3i = -- DKi

0 In ai*
O In el*

~ tj zt 01naj* ] ~ci
j~e.h
Zj O In ci*
~X

[9a]
=--DKi

(l--ti)

01nj__~*
0 In ci*

__

~j

j=2~i.e.h

z,

01naj* ] ~c,

Zj 0 In ci*

~x
[gb]

Vol. 124, No. I0

These equations give the flux d e n s i t y for a n y c h e m ical c o m p o n e n t a n d hold both for the ionic species
w i t h i n the solid or for t h e effective flux d e n s i t y of
such species in their n e u t r a l form. These equations
a r e distinct from those which a p p e a r e d in the e a r l i e r
discussion [7], however, in t h a t the a c t i v i t y and conc e n t r a t i o n terms only involve n e u t r a l chemical species,
and n e i t h e r electrons nor holes.
These g e n e r a l equations have a form s i m i l a r to
the f a m i l i a r F i c k ' s first l a w
Jl = - - D I

8Cl

[i0]

ax

w h e r e / ~ is the chemical diffusion coefficient

effective diffusion coefficient) for species i ( w i t h
erence to the c r y s t a l lattice, which in t h e cases
cussed below, is identical to the l a b o r a t o r y f r a m e )

~)i = DKi W

(the
refdisand
[11]

w h e r e the factor W is an e n h a n c e m e n t factor, defined

b y the q u a n t i t y in the square b r a c k e t s

w=

(1-t,)

157t

KINETIC PARAMETERS

8 in ai.___~*
8 In ci*

j:~i,e,h

zi O In a j* ]
Zj

,O In c]*

[12]
The s y m b o l W was selected for this p u r p o s e in honor
of Carl Wagner, who first showed (14) the influence
of the t r a n s p o r t of c h a r g e d species upon each other.
Di is sometimes called the "intrinsic diffusion coefficient" of species i, w h e n r e f e r r e d to the l a b o r a t o r y
frame. In the case that the c r y s t a l and l a b o r a t o r y
f r a m e s a r e identical, these quantities are the same.
I n cases in w h i c h two atomic species interdiffuse, the
t e r m "interdiffusion coefficient" is sometimes used w i t h
r e f e r e n c e to the c r y s t a l frame, which m a y move w i t h
respect to the l a b o r a t o r y frame.
In m a n y systems of p r a c t i c a l i m p o r t a n c e , including
t a r n i s h i n g processes (14), the situation is simplified
b y the fact that two types of species (either two different ionic species, or one ionic and one electronic
species) d o m i n a t e the t r a n s p o r t phenomena. U n d e r
this situation, the chemical diffusion coefficients of
the two species are equal, and we can use the s y m b o l
for both (15). F o r the case in which o n l y one ionic
and one elect}onic species have to be considered, so
t h a t te ---- 1 -- ti, the e n h a n c e m e n t factor becomes
O in ai*
W = r e - O In ci*

[13]

and
_- DKit e 0 I n ai_____~*

[14]

0 In ci*
If the s a m p l e is p r e d o m i n a n t l y an electronic conductor,
so that te --> 1, w e h a v e s i m p l y
O In ai*
W -- - 0 In ci*

[15]

and
5

-----

DK, O In ai__...~*

[16]

0 In ci*
This is the case p r e v i o u s l y discussed b y W a g n e r (16).
Using the definition of the a c t i v i t y coefficient "n =
ai/ci, the e n h a n c e m e n t factor can be w r i t t e n in the
form
W--J1
81n~t
Olnvi]
[17]
-t-a--~-~nc~]=[1 +c~ Oci
d e r i v e d for m e t a l s b y D a r k e n (17).

On the other hand, if the t r a n s f e r e n c e n u m b e r of

the ionic species is m u c h l a r g e r t h a n t h a t for the
electronic species, Eq. [13] can be r e w r i t t e n as
W =

(+:) 0oo,"

[18]

d In ci*

and b y using Eq. [2] and [5], we get

W --

ceD~e

8 in ai*

Zi2CiDKi

0 In ct*

[19]

and then
--

8 In ai*
0 In ci*

CeDKe

Zi2Ci

[20]

Thus we see that, in this case, the chemical diffusion

coefficient for the ionic species is d e p e n d e n t on the
component diffusion coefficient of the electrons, not
the ions.
Let us now f u r t h e r e x a m i n e the v a l u e of the enh a n c e m e n t factor for several different situations for
the common and i m p o r t a n t case in which only one
ionic s p e c i e s and one electronic species (assumed to
be excess or mobile electrons) have to be considered,
the t r a n s f e r e n c e n u m b e r s of all o t h e r species being
negligible. F r o m Eq. [8] and [13], the e n h a n c e m e n t
factor for the ions becomes s i m p l y

w =

[ O In ai

0 In ae

]j

[21]

F o r the special case in which we can assume t h a t

both the ionic species and the electrons obey either
H e n r y ' s or Raoult's law, i.e., "n and me are constant,
and considering the e l e c t r o n e u t r a l i t y condition

dCe -" zidci

[22]

we d e r i v e from Eq. [21]

W : te

1 -~ Zi2

[23]

'
Ce

We can thus conclude that if te ~

1, i.e., in the
case of a solid e l e c t r o l y t e w i t h dilute mobile ionic
species, W will tend t o w a r d zero, and the chemical
diffusion of ions in response to a composition g r a d i e n t
will be v e r y sluggish.
On the other hand, if electronic conduction p r e dominates, te --> 1, the v a l u e of W will d e p e n d sensit i v e l y upon the value of ci/ce. If ci < < ce, W will
a p p r o a c h unity, so the chemical diffusion coefficient
for the ionic species becomes the same as the component diffusion coefficient. If zi2ci = Ce, W becomes 2.
T h e r e are m a n y cases in which electronic conduction p r e d o m i n a t e s (ti < < 1), and y e t ci > > Ce. This
is possible if the electrons have a much g r e a t e r m o b i l i t y than the ionic species and can lead to u n u s u a l l y
l a r g e values of W, and thus of ~}i, as pointed out b y
W a g n e r (18), who cited a n u m b e r of m a t e r i a l s in
which this has been found. It will be shown l a t e r in
this p a p e r that this is also true for Li~Sb.
V e r y large e n h a n c e m e n t factors can also be p r e s e n t
for m a t e r i a l s in which one can assume that only the
electronic species e x h i b i t ideal solution behavior. In
t h a t case Eq. [21] becomes
F O In ai

w = tel

ci -1

+ Zi2 -

Ce

[24]

The large e n h a n c e m e n t (or reduction) factor W

is sometimes e x p l a i n e d in terms of a microscopic model
in which the m o r e mobile species tend to move ahead
of the others. If they h a v e different charges (or species
of the same sign m o v e at different rates in opposite
directions), this creates an i n t e r n a l electric field in
which the slower species are accelerated, and the

1572

J. E t e c t r o c h e m .

Soc.: S O L I D - S T A T E S C I E N C E A N D T E C H N O L O G Y

O c t o b e r 1977

Table I. Value of enhancement factor under various conditions

(Cases

Thermodynamic
assumptions

with only one ionic species and electrons mobile)

Concentration
assumptions

E n h a n c e m e n t factor

Transference

(W)

no. assumption

f
a.

General

General

t eL[ ~OIn ai + Zi- 8 in ae

81n ei

General
or

b.

General

General

t~ < < I

~lnci

tel Olnai" 1
<<

[01na,* ]
L c0 In
p a

C,

[a:

(const.) c!

General

(const.) c~]

General

or

tel1 + '1
te

d,

[al = (const.) cJ]

ae
(const.) ce

General

tl < <

e.

[a~ = (const.) ci]

ae (const.) Ce

ci < < co

tl

f.

[al = (const.) c~]

ae (const.) ce

l zi I ci = co

ti < < 1

g.

[a, = (const.) ct ]
ae (const.) Ce

cl > > ce

t~ < < 1

h.

[ Ion g e n e r a l c~ 1J
Lae (const.)

General

ti < < 1

faster ones retarded, in order to m a i n t a i n local charge

flux neutrality.
It should be mentioned that if the second t e r m in
either Eq. [23] or [24] is significantly greater than
unity, we should expect the t e m p e r a t u r e dependence
of the chemical diffusion coefficient to be different
from that of the component or tracer diffusion coefficients, due to the t e m p e r a t u r e dependence of cl/ce.
The values of the e n h a n c e m e n t factor W that are
expected u n d e r these various conditions are presented
in Table I.

Determination of the Chemical Diffusion Coefficient by

Use of the Galvanostatic Intermittent
Titration Technique
The chemical diffusion coefficient of species A and
other kinetic and t h e r m o d y n a m i c parameters m a y be
investigated in a mixed conductor Ay+~B, (5 symbolizes the deviation from the ideal stoichiometric composition) by the use of a galvanic cell with A~+sB
as one electrode, as shown in Fig. 1. Because of potential problems with electrode polarization, separate
counter (A) and reference (A ~ electrodes generally
have to be employed. Instead of pure A, another
material with a different activity of A m a y also be

I
___._o E

(D

AI

Ao I

A+ ELECTROLYTE
I
I

,
I

Fig. !. Schematic illustration of experimental galvanic cell arrangement. The electrolyte-sample interface is at x = O. The
sample thickness is L,

(~

1 + Zi2 ~

<< 1

DE.

DKI

Ce

1
I + Iz~l

I 0 In at

ci

used for these two electrodes. As will become obvious

later, the location at which the reference electrode is
attached to the electrolyte is u n i m p o r t a n t , e.g., the
l e f t - h a n d electrode m a y be divided into two parts,
and partially used as a counter and partially as a
re~erence electrode.
According to the Nernst equation
E =

kT
ZAq

In

aA* (A ~)

[25]

aA, (A N+ ~B)

the cell voltage E is thus a measure of the t h e r m o dynamic activity of n e u t r a l A in the Au+~B sample
at the interface with the electrolyte.
A n electric c u r r e n t I which is d r i v e n through the
galvanic cell by an external source determines the
transport of the relevant mobile ionic species within
the sample just inside the phase b o u n d a r y with the
electrolyte (where x = 0)
I = -- Sziq~) 0ci
OX

[2~6]

I x=0

with i being either A or B, depending on which one

has the p r e d o m i n a n t conductivity. S is the area of
the sample-electrolyte interface.
The principles u n d e r l y i n g this procedure for the
d e t e r m i n a t i o n of the kinetic and t h e r m o d y n a m i c parameters of a mixed conductor are illustrated in Fig.
2. Starting with a sample of k n o w n stoichiometric composition and with the galvanic cell in t h e r m o d y n a m i c
equilibrium, i.e., the concentrations of all species are
homogeneous throughout the electrode Au+~B, corresponding to cell voltage Eo, a constant c u r r e n t Io
is applied to the cell at time to by a galvanostat,
or simply by a b a t t e r y and a large resistor. According
to Eq. [26] this produces a constant concentration
gradient acl/Ox within the Ay+~B at the phase b o u n d ary with the electrolyte (x = 0). I n order to m a i n t a i n
this constant concentration gradient, the applied cell
voltage increases (or decreases, depending on the direction of the current) with time. A voltage step, corresponding to the I R drop due to the c u r r e n t flux
through the electrolyte and the interface is s u p e r i m posed, whose m a g n i t u d e depends on the position of
the reference electrode. However, it is always timeindependent (on the scale of this e x p e r i m e n t ) , and
acts as a constant that m e r e l y shifts the measured

VoL 124, No. 10

1573

KINETIC PARAMETERS

The solution of the differential Eq. [28] u n d e r conditions [29]-[31] is k n o w n (19, 20) and can be cast
in the following f o r m for x -- 0

Z
td
n,
n.

2Ion/t"

c,(x=0, t)=Co+ v - ziq

==

--

----'O

(ierfc[_~t

]_}_ierfc[ ' (nW1)L

to+V

to

= Time,

w i t h ierfc(~) = [ ~ - l / e e x p ( _ ~ 2 ) ] _ t + [~. erf(~.)],

the first i n t e g r a l of the c o m p l e m e n t of the e r r o r f u n c -

I.D

I~

tD
0>

.._1
JLI2
(D
I E0--

~ } I R

OROP

tion. A t times t < < L2//~ the infinite sum can be a p p r o x i m a t e d b y the first term. Then, we have for the
v a r i a t i o n of ci w i t h t h e square root of time

T \
L

._A

to

to+T

dci(x -- O, t)

~Time,

voltage b y a constant value b u t does not change t h e

g e o m e t r i c a l shape of the v o l t a g e - t i m e curve.
A f t e r a t i m e i n t e r v a l T, the c u r r e n t flux is i n t e r rupted, w h e r e u p o n the composition within the Au+~B
s a m p l e tends to again become homogeneous b y diffusion of the mobile species. During this e q u i l i b r a t i o n
process the surface composition of the sample, and
t h e r e f o r e the cell voltage, drifts b a c k t o w a r d a n e w
s t e a d y - s t a t e v a l u e El, corresponding to a new a c t i v i t y
of A in the s a m p l e as a result of the change of the
stoichiometry ~5 caused b y the coulometric t i t r a t i o n
of A ions into it b y the c u r r e n t
Io~MB

- -

[27]

ZAmBF

MB, roB, Io, and F are the atomic w e i g h t of B, the mass

of the c o m p o n e n t B in the sample, the constant c u r rent, and F a r a d a y ' s constant, respectively. A f t e r the
electrode is again in equilibrium, the p r o c e d u r e m a y
be repeated, starting now with t h e n e w cell voltage El.
This process m a y be continued until a phase change
occurs in the electrode, or the e l e c t r o l y t e decomposes
or becomes e l e c t r o n i c a l l y conductive.
In o r d e r to calculate the voltage E as a function
of time t d u r i n g w h i c h the c u r r e n t is applied, the time
d e p e n d e n c e of the concentration ci at the interface
x = 0 has to be d e t e r m i n e d b y solving Fick's second
law
~ c i ( x , t ) : ~ O~ci(x,t)
[28]
Ot
Ox2
with the initial and b o u n d a r y conditions
ci(x,t=O)
~
-- D

:Co

Oc~

Ox
Oci

==0
=0

(O<--x<=L)

[29]

Io

t3D]

(t>__0)

(t

<</~/D)

[33]

If changes of the m o l a r volume w i t h composition

m a y be neglected, the changes in the concentration
and the s t o i c h i o m e t r y are r e l a t e d t h r o u g h

Fig. 2. Schematic illustration of a single step of the galvanostatic intermittent titration technique (GITT). AEt is the total
transient voltage change of the galvanic cell for an applied galvanostatic current la for the time "c, AEs is the change of the
steady-state voltage of the cell for this step.

a8 :

2Io
=

IE 1

dci--

NA
- d~
VM

[~4]

w h e r e NA is A v o g a d r o ' s n u m b e r and VM is the m o l a r

volume of the sample. I n s e r t i n g this exPression in
Eq. [33] and e x p a n d i n g b y dE yields the following
expression for the expected time d e p e n d e n c e of the
cell voltage

dE

2V~Io

dE.

( t < < L~/D)

[35]

sr=,v
dE~d5 is the slope of the coulometric titration curve,
which is found b y plotting the s t e a d y - s t a t e voltages,
m e a s u r e d a f t e r each t i t r a t i o n step, against the c o m position, c a l c u l a t e d f r o m the c u r r e n t flux times the
applied time i n t e r v a l w i t h the help of Eq. [27]. W i t h
this information, the chemical diffusion coefficient
m a y be calculated from Eq. [35] because all other
quantities a r e k n o w n or m e a s u r a b l e

s
(t < < L21~))

[36]

If the e l e c t r o l y t e is in contact w i t h both sides of the

sample, e.g., in the case that a liquid e l e c t r o l y t e is
used, the m i d d l e plane, r a t h e r than the far side, of a
pellet s a m p l e is equivalent to the position x ---- L.
Because of s y m m e t r y , t h e r e will be no t r a n s p o r t of
species across this plane. In this case, the total a r e a
of contact b e t w e e n the e l e c t r o l y t e and the electrode
has to be t a k e n into account w h e n calculating the
a r e a S.
If b y using a sufficiently small c u r r e n t the change
of the s t e a d y - s t a t e ( e q u i l i b r i u m ) voltage (El -- Eo)
-~ AEs over a single g a l v a n o s t a t i c t i t r a t i o n is small,
dE/d5 m a y be considered to be constant and m a y be
r e p l a c e d by t h e ratio of the finite quantities, 5Es/a5.
Thus, by inserting Eq. [27] for the change of the
stoichiometry in Eq, [36] we h a v e

Sziq
(t>_-0)

[31]

The last condition is due to the fact that the r i g h t h a n d phase b o u n d a r y of the s a m p l e is assumed to be
impermeable,

[37]
This expression m a y be t r a n s f o r m e d once m o r e to an
even s i m p l e r algebraic form if E vs. ~/~ shows the
expected s t r a i g h t line b e h a v i o r over the entire t i m e
p e r i o d of the c u r r e n t flux

October 1977

J. Electrochem. Soc.: S O L I D - S T A T E S C I E N C E A N D T E C H N O L O G Y

1574

4 (mBVM~2(AEs~2

~rAte :

hEr is the total change of the cell voltage E d u r i n g the

c u r r e n t pulse, neglecting the IR drop.

Determination of Other Kinetic and

Thermodynamic Quantities

maVMIoAEs
MBS ~ ( AEt) a

(T < < L2/D)

[43]

Thus, like the chemical diffusion coefficient, the conductivity t e r m ~Ate m a y be d e t e r m i n e d from the change
in the s t e a d y - s t a t e voltage, AEs, and the m a g n i t u d e of
the voltage increase d u r i n g one titration, AEt.

Besides the d e t e r m i n a t i o n of the chemical diffusion

The component diffusion coeJ~cient, the mobilities,

and the tracer diffusion coeJ~cient.--For a p r e d o m i -

coefficient D, it is possible to e v a l u a t e o t h e r kinetic

and t h e r m o d y n a m i c p a r a m e t e r s b y use of the g a l v a n ostatic i n t e r m i t t e n t t i t r a t i o n technique. The m e t h o d s
for obtaining some of the m o r e i m p o r t a n t quantities
are as follows.

n a n t l y electronically conducting electrode containing

mobile AzA ions, DKA m a y be d e t e r m i n e d from Eq. [16]
using the expressions [39] and [36]-[38] for the e n h a n c e m e n t factor and the chemical diffusion coefficient,
respectively. As previously, if dE/d5 m a y be considered
as constant for a single t i t r a t i o n step, we have

The enhancement ]actor.~As discussed e a r l i e r the

chemical diffusion of species A is enhanced b y the
t h e r m o d y n a m i c factor 0 In aA*/O In CA* r e l a t i v e to the
component diffusivity. This e n h a n c e m e n t factor can
be d e t e r m i n e d f r o m the local slope of the coulometric
t i t r a t i o n curve, dE/dS, at a n y composition. The change
of In aA* is given b y the change of the voltage E of
the cell times zAq/kT, and the change in the concentration CA is NAdS/VM. Therefore, we h a v e
ZAqCAVM dE

0 In aA,

kTNA

0 In cA.

ZAq(y -t- 8)
kT

d8

dE
d5
[39]

By d e t e r m i n i n g the slope of the coulometric t i t r a t i o n

curve at different stoichiometries the t h e r m o d y n a m i c
factor m a y be obtained as a function of t h e composition.
The partial conductivity.--For the case in which the
chemical diffusion is p r e d o m i n a n t l y d e t e r m i n e d b y
one k i n d of ionic species, A z~ a n d either electrons or
holes, Eq. [14] yields, w i t h the substitution of DK
by ~ according to Eq. [2] and [5]
t A r e ' - - ( Z A q ) 2 C A D ( Oln aA* ) -1
kT
0 In CA*

ZAFD ( dE ~ - I

vM

\--~" /

4kTmBVMIo
~q2CAZA2MBS2T

__

AEs
( dE ~2

[41]

from which ~rAte m a y be calculated if the chemical

diffusion coefficient/~ has been d e t e r m i n e d as described
above. It is obvious that if the s a m p l e is p r e d o m i n a n t l y e l e c t r o n i c a l l y conducting, the p r o d u c t aAte is
the p a r t i a l ionic conductivity of the A species, CA. F o r
a p r e d o m i n a n t l y ionic conductor ~Ate is the p a r t i a l
electronic conductivity, ~e, since t e - - a e / ( ~ ' e -~- a A ) ~ 0"e/a"A.

If the coulometric t i t r a t i o n curve can be considered

l i n e a r over the r a n g e of a single galvanostatic t i t r a tion step, r e p l a c e m e n t of dE and d8 b y t h e i r finite

(t. <<: l.fl/D)

[44]
If, additionally, E vs. ~v~ is l i n e a r over t h e e n t i r e t i t r a tion period T, the component diffusion coefficient m a y
also be d e t e r m i n e d f r o m
DKA =

--

4kTmBVMIo
hEs
~CAZA2q2MBS2 (AEt) 2

('r < < L~/D)

[45]

The electrical mobility, UA, and the g e n e r a l mobility,

bA, a r e obtained from this expression b y use of the
N e r n s t - E i n s t e i n r e l a t i o n [5]. Also, it is possible to
calculate the t r a c e r diffusion coefficient DT from the
results of galvanostatic i n t e r m i t t e n t t i t r a t i o n e x p e r i ments i f an assumption can be m a d e concerning the
value of the correlation factor ]A (or m o r e generally,
the H a v e n ratio) (21)
DTA ----~~r

[40]

B y using Eq. [39] the t h e r m o d y n a m i c factor can be

replaced by a t e r m containing the slope of the coulometric t i t r a t i o n curve, dE/dS, which is d e t e r m i n e d
f r o m the s t e a d y - s t a t e values of the cell voltages in
b e t w e e n titrations and the corresponding change of
the composition. This yields
9

DKA =

[46]

The parabolic tarnishing rate constant.--If the r a n g e

of stoichiometry of the electrode m a t e r i a l is e x h a u s t e d
b y continual titrations, f u r t h e r ionic c u r r e n t t h r o u g h
the galvanic cell results in the g r o w t h of a second
phase outside the first one. The r e l e v a n t q u a n t i t y used
to describe the g r o w t h of such a l a y e r is the p a r a b o l i c
t a r n i s h i n g r a t e constant kt in cases in w h i c h the p r o c ess is d e t e r m i n e d b y b u l k diffusion. W h e n ions A ~A*
and either electrons or holes are the p r e d o m i n a n t l y
mobile species, {he ionic flux in the p a r a b o l i c a l l y g r o w ing l a y e r m a y be either described b y Fick's first law
w i t h the diffusion coefficient given by Eq. [14] or

dL'
kt
IJA[ = cA--~- = CA--~

[47]

if the a v e r a g e concentration CA m a y be r e g a r d e d as
a p p r o x i m a t e l y constant. L' is the instantaneous t h i c k ness of the t a r n i s h i n g layer. E q u a t i n g Fick's first l a w
and Eq. [47], and i n t e g r a t i n g over the thickness of
the layer, L', results in an equation from which the
p a r a b o l i c r a t e constant m a y be calculated as a function of the activity of A* or the compositional p a r a m eter 5 at the interface with the e l e c t r o l y t e ( x = 0)

values and using Eq. [37] for D yields

~At~ = --

VMmBIoAEs
M~SgT ( dE ~2
\ d%/-~ /

kt = ~
y

(t < < L2/~))

[42]
F u r t h e r m o r e , if z is also small c o m p a r e d to L2/D, i.e., E
is p r o p o r t i o n a l to X / t - o v e r the entire period of the
application of the constant c u r r e n t d u r i n g one t i t r a tion step, we have

Dd5

[48]

The i n t e g r a l is the a r e a u n d e r a plot of the chemical

diffusion coefficient, as d e t e r m i n e d b y galvanostatic
i n t e r m i t t e n t t i t r a t i o n using the t a r n i s h i n g p r o d u c t
(outer) phase as the electrode material, as a function
of the stoichiometric p a r a m e t e r 5 b e t w e e n the v a l u e
in e q u i l i b r i u m with the first (inner) phase and the
v a l u e at the outer surface. A l t e r n a t i v e l y , kt m a y be
calculated for a p r e d o m i n a n t l y electronic conductor

Vol. 124, No. 10

b y p l o t t i n g DKA, which is d e t e r m i n e d according to

Eq. [44] o r [45], as a function of the cell voltage E.
This follows from Eq. [48] b y using Eq. [16] for
and Eq. [39] for the e n h a n c e m e n t factor
k t -" ~

1575

KINETIC PARAMETERS

ZA

DKAdE

E vs.L[

[r.Vl

" L~ 3 Sb"

T = 3 6 0 *C

I = 2.5x IO-4 A/cm 2

800

[49]

The i n t e g r a t i o n extends from the voltage at t h e t w o phase e q u i l i b r i u m to the voltage corresponding to

the a c t i v i t y aA* or the stoichiometric p a r a m e t e r 5 for
w h i c h kt is evaluated.
I n c o n t r a s t to the usual t a r n i s h i n g e x p e r i m e n t s in
which the m a t e r i a l is t y p i c a l l y m a i n t a i n e d in contact
w i t h a constant a c t i v i t y of A*, e.g., t h a t c o r r e s p o n d i n g
to e q u i l i b r i u m w i t h a n o t h e r phase, the m e t h o d d e scribed h e r e p e r m i t s the t a r n i s h i n g r a t e constant to
be e v a l u a t e d as a function of the activity of A* over
the whole stoichiometric r a n g e of the t a r n i s h p r o d uct phase.
A p p l i c a t i o n to T r i l i t h i u m A n t i m o n i d e , Li~Sb

The g a l v a n o s t a t i c i n t e r m i t t e n t t i t r a t i o n technique
has been a p p l i e d to Li~Sb as a m o d e l electrode constituent. Its kinetic p a r a m e t e r s d e t e r m i n e the r a t e of
alloying a n t i m o n y w i t h l i t h i u m at high l i t h i u m activi.ties. Due to the Iarge a m o u n t (3 moles) of l i t h i u m
that can react p e r mole of antimony, this b i n a r y syst e m m a y be of p r a c t i c a l i n t e r e s t for application in
n e w types of high p o w e r d e n s i t y batteries, e i t h e r at
r o o m t e m p e r a t u r e (22, 23) or at e l e v a t e d t e m p e r a t u r e s .
F r o m the point of view of testing the g e n e r a l a p p l i c a b i l i t y of the galvanostatic i n t e r m i t t e n t t i t r a t i o n technique it should be p o i n t e d out t h a t Li~Sb a c t u a l l y
offers less t h a n o p t i m u m conditions, for it has a comp a r a t i v e l y n a r r o w r a n g e of s t o i c h i o m e t r y and a v e r y
c o m p o s i t i o n - d e p e n d e n t e n h a n c e m e n t factor.
A eutectic m i x t u r e of m o l t e n LiC1-KC1 salt (spectroscopically pure, A n d e r s o n Physics Laboratories, U r bana, Illinois) has been used as an e l e c t r o l y t e for
l i t h i u m ions in a set of e x p e r i m e n t s on the Li3Sb
phase. Both r e f e r e n c e and counterelectrodes w e r e c o m posed of the s o l i d - s t a t e t w o - p h a s e system of l i t h i u m s a t u r a t e d A1 and the a d j a c e n t p h a s e "LiAI," which
has a composition at the phase b o u n d a r y of about 47
atomic p e r c e n t Li. This system has a p o t e n t i a l a b o u t
300 mV less n e g a t i v e than p u r e liquid l i t h i u m at
400~
The LisSb electrode was p r e p a r e d b y coulom e t r i c t i t r a t i o n of l i t h i u m into an a n t i m o n y disk. T h e
electric leads w e r e m a d e of m o l y b d e n u m , which e x hibits a negligible solubility for lithium. The e x p e r i ments were conducted w i t h i n a V a c u u m / A t m o s p h e r e s
C o m p a n y recycling h e l i u m d r y box. No i m p u r i t y
effects were observed.
T h e voltage r a n g e of the existence of the Li3Sb
phase is b e t w e e n about +0.88 and 0V w i t h reference
to p u r e l i t h i u m at 400~ This corresponds to a r a n g e
of l i t h i u m a c t i v i t y f r o m about 2.6 X 10 - 7 to 1. F i g u r e
3 shows a typical v o l t a g e - t i m e d e p e n d e n c e for the case
of g a l v a n o s t a t i c a l l y t i t r a t i n g l i t h i u m into the Lis+aSb
s a m p l e with a c u r r e n t d e n s i t y of 0.25 m A / c m 2, a p p l i e d
for 300 sec at 360~ The corresponding change of the
stoichiometric p a r a m e t e r ~ of the s a m p l e is about 2.5
X 10 -4. The voltage is p l o t t e d as a function of the
square root of time for the same m e a s u r e m e n t in Fig.
4. In a g r e e m e n t with theoretical considerations (Eq.
[35]), a s t r a i g h t line is observed for times up to 200
sec. The deviation from l i n e a r i t y at longer times is
discussed later.
A sequence of selected galvanostatic titrations of
l i t h i u m out of Li~Sb, d i s t r i b u t e d over the entire r a n g e
of the t h e r m o d y n a m i c existence of the compound, is
plotted in Fig. 5. The polarization of the voltage is
o b s e r v e d to be much g r e a t e r in the center of the
stoichiometric r a n g e of existence t h a n n e a r both ends.

700

I00

20O

300

Fig. 3. Typical transient voltage change of the galvanic cell

with a Li3Sb sample after a constant current of 2.5 X 10 - 4 A
cm2 was applied. LiCI-KCI(e) was used as a molten salt electrolyte,
and two-phase AI, LiAI mixtures used as counter and reference
electrodes.
t [sec]
0

I0

30

120

60

ISO

240

300

E vsLL

"L~,3 Sb"
T=360~C
I:2.5x10 - 4 A / c m 2
700

L__~L

12

16

Fig. 4. Representation of the transient voltage of the galvanic

cell as a function of the square root of the time. The experimental
conditions were the same as those of Fig. 3.

This is closely r e l a t e d to the shape of the coulometric

titration curve, d e t e r m i n e d from the s t e a d y - s t a t e cell
voltages observed b e t w e e n titrations as a function of
composition. The d a t a for s e v e r a l runs (in b o t h compositional directions) a r e shown in Fig. 6. N e a r the
m i d d l e of the composition r a n g e the slope dE/d8
has a m a r k e d m a x i m u m , p r o d u c i n g the greatest
changes of the t r a n s i e n t voltage w i t h time, in accordance with Eq. [35].
The t h e r m o d y n a m i c e n h a n c e m e n t factor, a In au/O
In cu, was calculated from the slope of the coulometric t i t r a t i o n curve and plotted in Fig. 7 as a function of the stoichiometry. As can be seen, the c h e m ical diffusion of the l i t h i u m is enhanced b y up to a
factor of n e a r l y 70,000 r e l a t i v e to the component d i f fusion coefficient (or the t r a c e r diffusion coefficient
divided b y the c o r r e l a t i o n f a c t o r ) .
In o r d e r to f u r t h e r test this technique, s e v e r a l a d ditional p a r a m e t e r s have been varied, a n d t h e results
c o m p a r e d w i t h the theoretical considerations. A t the
same voltage, or stoichiometric composition, the values
of the kinetic p a r a m e t e r s should be i n d e p e n d e n t of
the direction of the c u r r e n t flux. The slopes of the

J. EIectrochem. Sot.: S O L I D - S T A T E

i@76
E vB. Li

Imv]

71

--

8
r

" Li3 S'b"

T 800

October 1977

SCIENCE AND TECHNOLOGY

74.98
j

d (n qLi

Li3+~Sb

d ~13 CLL

T = 560~

at. % LL

75
t

7,5.02
i

Iq
-1 d E

Eg

IV]

x 1 0-2

X 1 0 -4
60C

6
-

I0

40C

T = 360~
I = 5xlO-4A
S = 1.5cm a

20C

4
- -i 6

io00

r r

II

io00

I0o o

qO0 0

ICE) 0

tq

I00 o
- t

~30

rsecl
L
J

Fig. 5. The transient voltages of the galvanic cell containing

Li3Sb as a function of the time t for several different initial steadystate voltages plotted vs. pure lithium using the same galvanostatic
current density of 3.3 X 10 - 4 A cm - ~ contact area between the
electrolyte and the sample. The different starting voltages represent different stoichiometries of Lia+~Sb as determined from
Fig. 6.
~ o t . %
74,98
I000
E

vs.

75

Li,
75.02

Li.

T - 360 ~

[mY]

6OO

800

/
f
x

2
"X~x~

i
-4

/i

-2

rx

x~x~

8 X 1 0 3 in L i 3 + a S b

Fig. 7. The composition dependence of the enhancement factor

in Li3+aSb, which causes the chemical diffusion coefficient to be
much greater than either the component diffusion coefficient or
the tracer diffusion coefficient of lithium. The enhancement factor
is determined from the slope of the coulometric titration curve
(Fig. 6), which is plotted at the right-hand ordinate.

E vs.
A~ ~'Li. Af'

[mv]
4OO

0
8 0 0 FE vs. L~

iO
I

20
I

40
,

60
I

80

I00

6OO

200

4O0

7OO
x
0
LL3Sb
T = 360 ~

2OO

I = 3.3X10 -4 A/cm 2
-200
600

I
0

0
-4

L
-2

I
0

L
2

- 3x103

I
4

in LL3+ ~ Sb

Fig. 6. The steady-state voltages of the galvanic cell with a

LisSb sample vs. pure lithium and an AI, LiAI electrode as a
function of the stoichiometry q3, i.e., the amount of lithium which
is electrochemically pumped into the sample (coulometric titration curve). The horizontal part of the curve represents the twophase region of Li~Sb in equilibrium with Li~Sb.

E vs. v'-t curves should be the same but of opposite

sign for the s a m e current density. This was found to
be true, as demonstrated in Fig. 8. Also, the calculated kinetic quantities should be i n d e p e n d e n t of the
actual value of the current. According to Eq. [35] the
slope of the plots of the voltage vs. the square root of
t i m e should be proportional to the current Io applied.
The results of e x p e r i m e n t s carried out w i t h current
densities differing b y a factor of 12 are s h o w n in
Fig. 9. Good agreement b e t w e e n experiments and
theory is seen.
The c h e m i c a l diffusion coefficient that was calculated f r o m the slope of the straight line in Fig. 4 and

I
2

I
4

'
6

I __

I0

,/T [~ec ~]
Fig. 8. Two transient voltage changes of the galvanic cell with
a li~Sb electrode with reference to pure lithium as a function of
the square root of time for adding lithium to the sample and removing it with the same current density at about the same mean
composition, i.e., cell voltage. The absolute value of the slopes
is seen to be the same for both procedures.

the corresponding change of the steady-state cell voltage according to Fig. 6 is ~ ~ 2 X l0 - s c m 2 sec -1 at the
stoichiometric deviation 6 ~ -- 6 X 10 -4 and 360~
This value is strongly enhanced by the e n h a n c e m e n t
factor of a In aL|/O In CLi = 1.3 I04, thus being related to a m u c h l o w e r component diffusion coefficient,
DKLi ~ 1.5 10 -9 cm2 sec-Z at the s a m e stoichiometry
and temperature. The tracer diffusion coefficient has
also the same order of magnitude, since the correlation factor is of the order of 1. The corresponding
partial l i t h i u m ionic conductivity was calculated to
h a v e a value of ~Lt : 1.5 X 10 -4 f1-1 cm-Z for that
composition, according to the general equations of
the previous section. Using the N e r n s t - E i n s t e i n equa-

Vol. I24, No. 10

,o

E-E

T=560~

(t=O)i

[mY]

2o

EI,:O.~

4o

6o

/4mA

8o

,oo

.oo / / /
~OO

I0

Fig. 9. The transient voltage of the galvanic cell with a Li3Sb

sample referenced to an initial ceil voltage of approximately 550
mV v s . pure lithium as a function of the square root of time. The
results are shown for several current densities. The slopes increase
almost linearly with the current density.

tion the general l i t h i u m mobility was found to be bLi

= 2 101' cm 2 V -1 A -1 sec -2, and the electrical
l i t h i u m mobility is ULi -- 3 10 - s cm 2 V -1 sec -1 at
this composition. The parabolic rate constant kt for the
formation of a Li~Sb t a r n i s h i n g layer on a Li2Sb (24,
25) substrate is of the order of 10 - s cm 2 sec -1 at a
l i t h i u m activity aLi "-- 4 X 10 -7 and of the order of
10 -7 cm 2 sec -1 at a l i t h i u m activity aLl .---- 1.
By use of this same procedure, values of the chemical diffusion coefficient D have been d e t e r m i n e d over
the whole r a n g e of stability of the Li3Sb phase, as
illustrated in Fig. 10.
Extensive experiments utilizing this galvanostatic
i n t e r m i t t e n t titration technique to study the systems
L i - S b and Li-Bi will be reported elsewhere (25, 26).
Discussion

The galvanostatic intermittent titration method combines transient and steady-state electrochemical measurements. In one set of experiments a n u m b e r of
kinetic and thermodynamic quantities m a y be readily
determined with considerable precision as a function
of composition within a single phase. The compositional resolution in this technique is quite high, so
that phases with only small ranges of stoichiometry
can be investigated. The experimental equipment requirements are quite modest, consisting p r i m a r i l y of
Jog 5

T = 360~C

-4'.4

o
o

/
/
c{

o
/

~.. . o. . ~

-52

-l

d6
dV~

2VMIo

(t < < L2/D)

[50]

SFziv~

vs. k/~ plot. A n e q u i v a l e n t procedure is to divide the

-48

a constant c u r r e n t source and an i n s t r u m e n t that can

m e a s u r e voltage vs. time.
The i n f o r m a t i o n that is obtained from the observation of the time dependence of the cell voltage d u r i n g
a galvanostatic c u r r e n t pulse is in principle no greater
than that which can be obtained by using other t r a n sient methods. However, e x p e r i m e n t a l problems in
other techniques related to resistance polarization,
which are typically only reduced by the use of reference ~lectrodes, are here totally eliminated.
In the common potentiostatic voltage step method,
the c u r r e n t should theoretically be infinite in the first
moment. This is not e x p e r i m e n t a l l y realizable, and
the imposed voltage difference creates large t r a n s i e n t
polarization effects. Thus the initial and b o u n d a r y
conditions usually applied to the assumed solution of
Fick's second taw are not exactIy fulfilled. The result
is a deviation from the theoretically expected l i n e a r
relation between the c u r r e n t and 1 / x / t at short times.
Additionally, because of the inverse time scale, this
part of the plot is expanded whereas the part with
the more useful i n f o r m a t i o n is compressed. In the case
of the galvanostatic titration method, however, the
initial period contains the most v a l u a b l e i n f o r m a t i o n
because any effects due to a change i n the e n h a n c e m e n t factor or to the finite thickness of the sample
do not become i m p o r t a n t u n t i l later. This early part
of the e x p e r i m e n t is fortuitously expanded by the use
of the square root of time scale in the voltage plot.
If a deviation from the linear dependence of the
voltage on the square root of time is found at longer
times in galvanostatic experiments it m a y have one
or more of several explanations. Either the solution
to the assumed boundary value problem is not valid
at long times because of finite length effects due to a
high diffusion coefficient or a thin sample, or there
m a y be a significant change of either the thermodynamic enhancement factor or the chemical diffusion
coefficient over the pertinent stoichiometric range.
These different possibilities m a y be evaluated from
the experimental results on the magnitude and composition dependence of the chemical diffusion coefficient and the enhancement factor. If necessary, a
current pulse of shorter duration or a smaller value
of current might be used.
Another w a y to eliminate the influence of a composition-dependent enhancement factor is to determine the stoichiometry 5 from the measured cell voltage E by using data from the coulometric titration
curve and to plot 5 as a function of k/t. According
to Eq. [35] the following relation should be found

Then, ~ m a y be d e t e r m i n e d from the slope of the 5

LL 3 Sb
-4

1577

KINETIC PARAMETERS

_ -oo I

I~
-0,5

__

0.5
~ x l O ~ in Li.3

Fig. 10. Variation of the chemical diffusion coefficient with

composition over the whole range of stability of Li3Sb at 360~

measured cell voltage by the corresponding t h e r m o dynamic factor and to plot this q u a n t i t y as a f u n c t i o n
of k / ~ However, because of the large variation in the
values for diffusion coefficients, often only an order
of m a g n i t u d e estimate is of interest, and these refinemeats m a y not be necessary.
E x p e r i m e n t a l errors might appear if the electrochemically active species are not exclusively used to
change the stoichiometry of the sample d u r i n g the
titration, but, after being discharged and becoming
neutral, diffuse back into the electrolyte or diffuse
into the electrical lead connected to the sample. These
possibilities could be checked in a separate experim e n t with a b l a n k sample, operating over the same
voltage range.
In conclusion, it has b e e n demonstrated that the
galvanostatic i n t e r m i t t e n t titration technique is a pow-

1578

J. Electrochem. Soc.: S O L I D - S T A T E S C I E N C E A N D T E C H N O L O G Y

erful tool which can be e m p l o y e d to d e t e r m i n e a n u m b e r of i m p o r t a n t kinetic a n d t h e r m o d y n a m i c quantities

in m i x e d conductors. Of special interest is its r e a d y
a p p l i c a t i o n to compounds w i t h small stoichiometric
ranges and a p p r e c i a b l e v a r i a t i o n of the t h e r m o d y n a m i c
e n h a n c e m e n t factor w i t h composition,
The values of chemical diffusion coefficient observed
in the case of LiaSb are s e v e r a l orders of m a g n i t u d e
g r e a t e r t h a n those found necessary to p r o d u c e n e g ligible diffusional polarization in fine p a r t i c l e b a t t e r y
electrodes.

Acknowledgments
This w o r k was funded by a g r a n t from the I n s t i t u t e
for E n e r g y Studies at Stanford University, w h i c h has
s u p p o r t e d one of the authors (W. W.) on a S t a n d a r d
Oil of California visiting professorship. The e a r l i e r
g r a n t of a NATO Scholarship t h r o u g h the G e r m a n
A c a d e m i c Exchange Service (DAAD) is also g r a t e fully acknowledged.
M a n u s c r i p t s u b m i t t e d March 14, 1977; revised m a n u script received M a y 23, 1977.
9 A n y discussion of this p a p e r will a p p e a r in a Discusstun Section to be published in the June 1918 JOURNAL.
All discussions for the June 1978 Discussion Section
should be submittedby Feb. 1, 1978.

Publication costs of this article were assisted by

Stanford University.

ai
bi
ct
~)i

LIST OF SYMBOLS
activity of species i
g e n e r a l m o o l l i t y Of species i (am 2 sac -2 V - 1 A - z )
concentration of p a r t i c l e i ( c m - ~ )

chemical diffusion coefficient of species i (am 2

sea-l)
DKi component diffusion coefficient of species i (am 2
sac -1)
DTi t r a c e r diffusion coefficient of species i (am 2
sea-l)
E
galvanic cell voltage (V)
aE~ s t e a d y - s t a t e voltage change (V)
AE~ transient voltage change iV)
]
correlation factor
F
F a r a d a y ' s constant, (A sac v a l - : )
I
electric c u n e n t (A)
Io
applied constant electric c u r r e n t (A)
Ji
flux density of particles i ( a m - 2 s e a - l )
k
Boltzmann's constant (V A sac ~ -1)
kt
p a r a b o l i c t a r n i s h i n g rate constant (cm 2 s e c - D
L
s a m p l e l e n g t h (cm)
mi
mass of species i (g)
Mi
atomic weight of species i (g m o l e - l )
NA A v o g a d r o ' s n u m b e r (mole -1)
q
e l e m e n t a r y charge (A sac)
S
contact area between electrolyte and sample
(am 2)
t
time (sec)
t~
t r a n s f e r e n c e n u m b e r of species i
T
absolute t e m p e r a t u r e (~
u~
electrical m o b i l i t y of species i (am z V -1 s e a - l )
V ~ m o l a r volume (cm a mole - I )
W
e n h a n c e m e n t factor
x
distance coordinate (cm)

y
zi
"n
5
Tn
m
m~
r
r

October I977

stoichiometric n u m b e r
vMence of species i
activity coefficient of species i (era 3)
deviation f r o m t h e (ideal) stoichiometry
electrochemical p o t e n t i a l of species i (per p a r ticle) (V A sac)
chemical p o t e n t i a l of species i (per p a r t i c l e )
(V A sec)
chemical potential of species i in the s t a n d a r d
state (V A sac)
p a r t i a l electrical conductivity of species i ( ~ - 1
CITI-1)
pulse d u r a t i o n (sec)
electrostatic p o t e n t i a l (V)

REFERENCES
1. W. F. Chu, H. Rickert, and W. Weppner, in "Fast
Ion T r a n s p o r t in Solids, Solid S t a t e Batteries and
Devices," W. van Gool, Editor, p. I8I, N o r t h Holland Publishing Co., A m s t e r d a m - L o n d o n (1973).
2. H. R i c k e r t and W. W e p p n e r , Z. Natur]orsch., Tell A,
29, 1849 (1974).
3. B. C. H. Steele, in "Mass T r a n s p o r t P h e n o m e n a in
Ce ramlcs,
" " A. R. Cooper and A. H. Heuer, E d i tors, p. 269, P l e n u m Press, New Y o r k (1975).
4. J. B. Wagner, Jr., in "Electrode Processes in Solid
S t a t e Ionics," M. Kleitz and J. Dupuy, Editors,
p. 185, D. Reidel, D o r d r e c h t (1976).
5. H..Rickert, in "Electromotive Force M e a s u r e m e n t s
m H i g h - T e m p e r a t u r e Systems," C. B. Alcock,
Editor, p. 59, The Institute of Mining and M e t a l lurgy, London (1968).
6. R. A. Rapp and D. A. Shores, in "Techniques of
Metal Research," Vol. 4, P a r t 2, R. A. Rapp, E d i tor, p. 123, Interscience, N e w Y o r k (1970).
7. D. O. Raleigh, Electroanal. Chem., 6, 87 (1973).
8. R. N. Adams, " E l e c t r o c h e m i s t r y at Solid Electrodes," M. D e k k e r inc., New York (1969).
9. A. J. Rosenburg, This Journal, 107, 795 (1960).
10. E. Fryt, S. Mrowec, and T. Walec, Oxid. Met., 7, 117
(1973).
11. S. Mrowec, J. Mater. Sci., 9, 1961 (1974).
12. C. Wagner, in "Progress in Solid S t a t e Chemistry,"
Vol. 10, P a r t 1, J. McCaldin and G. Somorjai, E d i tors, p. 3, P e r g a m o n Press, Oxford (1975).
13. R. Haase, "Transportvorg~nge," Steinkopff Verlag,
D a r m s t a d t (1973).
14. C. Wagner, Z. Phys. Chem., Abt. B, 21, 25 (1933).
15. C. Wagner, Acta Metall., 17, 99 (1969).
16. C. Wagner, in "Atom Movements," p. 153, A m e r i c a n
Society for Metals, Cleveland, Ohio (1951).
17. L. S. Darken, Trans. AIME, I75, 184 (1948).
18. C. Wagner, J. Chem. Phys., 21, 1819 (1953).
19. H. S. Carslaw and J. C. Jaeger, "Conduction of Heat
in Solids," p. 112, Clarendon Press, Oxford
(1967).
20. J. Crank, "The Mathematics of Diffusion," Oxford
U n i v e r s i t y Press, London (1967).
21. J. B a r d e e n and C. Herring, in " A t o m Movements,"
p. 87, A m e r i c a n Society for Metals, Cleveland,
Ohio (1951).
22. J. O. Besenhard and H. P. Fritz, Electrochim. Acta,
20, 513 (1975).
23. Rheinisch-Westf~lisches E l e k t r i z i t ~ t s w e r k AG, Fr.
D e m a n d e 2,206,593 (1974); Get. AppL P. 2,254,870.5 (1972).
24. R. G~rardin and J. A u b r y , C. R. Acad. Sci., Set C,
278, 1097 (t974).
25. W. W e p p n e r and R. A. Huggins, To be published.
26. W. W e p p n e r and R. A. Huggins, S u b m i t t e d to
J. SoLid State Chem.