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MIXED IONIC-ELECTRONIC CONDUCTIVITYOF Lal-xSrxCol-yFey03-6

PEROVSKITE-TYPE OXIDES

Y. Teraoka, H.M. Zhang, K. Okamoto, and N. Yamazoe

Department of Materials Science and Technology, Graduate School of
Engineering Sciences, Kyushu University, Kasuga, Fukuoka 816, Japan

( R e c e i v e d J u l y 31, 1987; C o m m u n i c a t e d b y M. Koizumi)

ABSTRACT Ionic (ai) and electronic (Oe) conductivities of mixed conduc-

t i v e Lal-xSrxCol-yFey03-6 were separately measured by means of four-
probe ionic dc and ordinary four-probe dc techniques, respectively.
At 1073 K, f o r instance, ai ranged in the order of I - 10-2 S cm-1
while ae was around 102 S cm-1, indicating that the present oxides
were good mixed conductors with ionic transport number 10-2 - 10-4.
ai increased as contents of Sr and Co increased though Sr content was
more i n f l u e n t i a l . The apparent a c t i v a t i o n energy f o r oxide ion
conduction as well as the dependences of ai on oxide composition and
oxygen partial pressure suggested that oxide ion conduction occurred
via a vacancy mechanism. The relation of mixed conductivity to the
oxygen semipermeability was also discussed.
MATERIALS INDEX: perovskites, oxides, lanthanum, strontium, cobalt,
iron

Introduction

Some highly nonstoichiometric oxides show mixed c o n d u c t i v i t y by both

ionic and electronic charge carriers, and mixed conductors have increasingly
attracted great attention in many practical applications (i). So far, mixed
conduction by oxide ions and electrons (or holes) have been reported in many
oxide systems such as Bi203-Tb203.5 (2), ZrO2-CeO2-Y203 (3), among which oxy-
gen-deficient perovskite-type oxides containing transition metals at B sites,
e.g., Lal-xSrxCo03-6, seem to be prominent mixed conductors with high ionic
and e l e c t r o n i c c o n d u c t i v i t i e s . Although LnCo03 (Ln: rare earth element)
i t s e l f has been known to show high e l e c t r o n i c c o n d u c t i v i t y , the p a r t i a l
substitution of Sr2+ for Ln3+ brings about not only an increase in electronic
conductivity but also an appearance of ionic conductivity by the concomitant
f o r m a t i o n of Co4+ (or hole) and oxide ion vacancies, r e s p e c t i v e l y . This
e f f e c t appears to c o r r e l a t e i n t i m a t e l y with the high performance of the
oxides as catalysts in electrode process (4) or in complete oxidation cataly-
sis (5,6), e l e c t r o d e m a t e r i a l of fuel c e l l (7), gas sensor (8), etc. On the
other hand, the substitution for the B site element was also reported to give
51
52 Y. TERAOKA, et al. Vol. 23, No. 1

rise to promotive effects. For example, the substitution of Fe for Co of

Lal-xSrxCo03-6 reportedly enhanced the sensitivity of a combustion monitoring
sensor (9) and the catalytic activity for electrochemical reduction of oxygen
(4). We recently reported that La1-xSrxCo1%yFey03-6 showed excellent oxygen
semipermeability at elevated temperatures (10). All these properties, i.e.,
catalytic activity, electrode activity, gas s e n s i t i v i t y , oxygen semiperme-
a b i l i t y etc., are deeply related with the mixed conduction of the perovskite-
type oxides. However, there have been few reports which evaluated their
mixed conductivities.

This paper aims at evaluating mixed conductivities of Lal-xSrxCol-y-

FeyO3-a as functions of temperature and A-site as well as B-site composi-
tions. I t also aims at establishing relations between mixed conductivities
and the oxygen semipermeability.

Experimental

Lal-xSrxCol-yFey03-~ were prepared from JIS special grade reagents of

lanthanum, strontium, cobalt acetates and iron nitrate. An aqueous solution
dissolving starting materials in a desired proportion was evaporated to
dryness, followed by the calcination at 1123 K in air for 10 h. The powder
of each sample thus obtained was compressed into a disc, 20 mm diameter and 4
mm thick, under the hydrostatic pressure of 260 MPa. After the disc was cut
into a rod, approximately 4 x 4 x 12 mm, the specimen was sintered at 1473 K
or 1523 K (for Fe containing samples) in air for 5 h. The obtained specimen
was polished by an emery paper before subjecting conductivity measurements.
(YOI.5)O.16(Zr02)O.84 (YSZ) was prepared from Y203 (99.99%) and Zr02 (99.9%).
A mixture of Y203 and Zr02 was f i r s t
calcined in a i r at 1573 K for 5 h.
The pre-calcined oxide was ground,
pressed hydrostatically (260 MPa) in
a disc, 10 mm diameter and 2 mm
thick, and sintered in air at 1723 K
for 15 h. ionic current
e~de

Oxide ionic conductivity of

Lal-xSrxCol-yFey03-~ was measured by
means of a four-probe ionic dc tech-
nique. The cell arrangement is
schematically shown in Fig. I. For
having a pure ionic current supplied
to and taken out from the sample
specimen, ionic current electrodes,
Pt / Lao.2SrO.8Coo.sFeo.203-6 / YSZ, [] sample • Pt plate
were contacted to the both ends of [] mixed conductor
the specimen mechanically as shown. (Lao.2Sro.8Coo.8Feo.203_a)
Under a flow of constant current, I,
voltage drop, V, across the specimen El solid electrolyte
was measured by the ionic probes, 3 ((YOi.5)o.16(Zr02)o.84)
mm apart for each, which had essen-
t i a l l y the same construction as the FIG. I
ionic current electrode with their Schematic cell arrangement of four-
sharp edges coming into contact with probe ionic dc measurement.
Vol. 23, No. 1 PEROVSKITE-TYPE OXIDES 53

the s i d e o f the specimen m e c h a n i c a l l y . Oxide i o n i c c o n d u c t i v i t y ( o i ) was

c a l c u l a t e d from the f o l l o w i n g equation.

oi : I I/V S [1]

where 1 and S are the distance between i o n i c probes and the c r o s s - s e c t i o n a l

area of the sample specimen, r e s p e c t i v e l y . The constant current I was regu-
lated in a range of I - 10-2 mA so as to give a s t e a d y - s t a t e voltage d i f f e r -
ence of I - I0 mV. The c o n d u c t i v i t y measurement c e l l was placed in a quartz-
glass equipped in an i n f r a r e d image furnace. The c e l l was heated up to 1150
K at a r a t e of I0 K min-1 and holded a t t h a t t e m p e r a t u r e f o r 30 min in an
atmosphere of He, a i r or 02. Then the c e l l was cooled stepwise at a rate of
5 K m i n - i to t e m p e r a t u r e s a t which i o n i c c o n d u c t i v i t y was measured a f t e r
holding f o r 30 min to e q u i l i b r a t e the temperature of the specimen with t h a t
of s u r r o u n d i n g . To reduce the e f f e c t s of p o l a r i z a t i o n , measurements were
s u c c e s s i v e l y c a r r i e d out in both forward and reverse d i r e c t i o n s of current.
The measurement of e l e c t r o n i c c o n d u c t i v i t y (Oe) was c a r r i e d out by an o r d i -
nary four-probe dc technique in a i r .

Temperature programmed desorption (TPD) of oxygen was c a r r i e d out in a

stream of He f o r Lal-xSrxCoO.4Feo.603-6 at a heating rate of 10 K m i n - l . The
procedure was described elsewhere (6).

Results and Discussion

Effects of temperature on
~iVTties
1°3l
102 O-e(air)
In Fig. 2, i o n i c ( d i )
and e l e c t r o n i c (~e) conduc- 10o
tivities o f LaO.8SrO.2-
Co0.8Fe0.203-~ under s e v -
eral surrounding atmo-
s p h e r e s a r e shown as a I0 -I
f u n c t i o n of t e m p e r a t u r e .
For measurements of o i , the (,I)
~ c i (He)
l o w e r l i m i t of measuring
t e m p e r a t u r e , 800 K, was b
d e t e r m i n e d by the i o n i c 10 -2
0~" CT
c o n d u c t i v i t y o f YSZ which
was used as an e l e c t r o n
b l o c k i n g m a t e r i a l o f the
ionic current electrode. 10 -3
oi o f LaO.8Sr.2Co.8Fe.203-~
increased with decreasing
oxygen p a r t i a l pressure
(P02) of the s u r r o u n d i n g 10-4 , ,~ ,
atmosphere, 02 < a i r < He. 0,8 0,9 1.0 i,i 1,2 1,3
In e v e r y case, however, oi
was l a r g e r by about one T-1 /I0-3 K-I
o r d e r o f m a g n i t u d e than
t h a t of YSZ a t the same FIG. 2
temperature as d e p i c t e d Temperature dependence of i o n i c and e l e c t r o n i c
t o g e t h e r i n Fig. 2. This c o n d u c t i v i t i e s of Lao.8Sr.2Coo.8Feo.203-8.
54 Y. T E R A O K A , et al. Vol. 23, No. 1

confirms that the perovskite-type oxide is an excellent oxide ion conductor.

The observed e f f e c t s of P02 can be understood from the oxygen-sorptive prop-
e r t i e s of the oxide. As d e s c r i b e d in more d e t a i l l a t e r , a l a r g e amount of
oxygen can be desorbed from or absorbed in the c r y s t a l l i n e l a t t i c e of the
oxide on heating or c o o l i n g , r e s p e c t i v e l y . This d e s o r p t i o n or a b s o r p t i o n
n a t u r a l l y r e s u l t s in f o r m a t i o n or e x t i n c t i o n of oxide ion vacancies (6).
Therefore, the concentration of oxide ion vacancies depends on P02 and tem-
p e r a t u r e . The observed decrease in ai w i t h i n c r e a s i n g POp can thus be a t -
t r i b u t e d to a decrease in 6, i f one assumes oxide ion c o n d u c t i o n via a
vacancy mechanism. I t is also noted from Fig. 2 that the apparent a c t i v a t i o n
energy f o r oxide ion conduction, Ea, increased with increasing POp. This was
again affected by oxygen sorption: in oxygen-containing atmosphege, the heat
of oxide ion vacancy formation was a d d i t i v e l y included in Ea.

I t was found that ae was larger by several orders of magnitude than oi

and l i t t l e dependent on PO2. The magnitude of Oe as well as its monotonous
decrease with increasing temperature suggest a metallic conduction. With
such high ionic as well as electronic conductivities, the present perovskite-
type oxide is concluded to be an excellent mixed conductor.

Effects of composition on conductivities

Effects of A s i t e (x) or B s i t e (y) s u b s t i t u t i o n on oi and ~e at 1073 K

are shown in Fig. 3. oi increased sharply with increasing x while i t gradu-

102 % 102

I !
E E
i0 0

b
ZLZf. ° oo i0°
b
y (air)
10-2 10 -2 (02 )

I I I ! I !
0 0,5 1.0 0 0,5 1.0
in Lal_xSrxCoo.8Feo. 203_6 Y In Lao.6Sro.4COl_yFey03_ 6

FIG. 3
Effects of A ( l e f t ) and B (right) site substitution on conductivities
at 1073 K of Lal-xSrxCol-yFey03-6.
Vol. 23, No. 1 PEROVSKITE-TYPE OXIDES 55

a l l y decreased with increasing y. I t is clear that ~i is p r i m a r i l y con-

t r o l l e d byA s i t e composition. Such dependences of oi on x and y coincide
well with the oxide ion conduction via a vacancy mechanism as shown below.
As f o r Oe measured in a i r , i t depended only s l i g h t l y on x with a modest
maximum at x = 0.4 - 0.6, while i t monotonouly decreased as y increased. The
dependences of Oe on x and y are essentially in accordance with the results
by Obayashi and kudo (14) and Rao et al. (15), respectively. From ~i and ae,
the ionic transport number of Lal-xSrxCol-yFey03-~ at 1073 K is calculated to
f a l l in the range 10-2 - 10-4 at the compositions examined.

% 20
>
E
/,..,,.;.;
. "....
]..,../ ,.,
#
C.)
oO
c-
O
C).
0')
10
(P

'El
if-<.
-I:-./.. ---:-
4 "

.................
..-: .....

0 /:,2: .......... 2 .......... -

0 ,i'd.,; . . . . . . I. . . . . . . . . . . . . . .I. . . . . . . . . . . . . . .I ~ i
(J

r~ I

300 500 700 900 1100

Temperature / K
FIG. 4
TPD chromatograms of oxygen from Lal-xSrxCoO.4FeO.603-~.
1. x = O, 2. x = 0.2, 3. x = 0.4, 4. x = 0.6, 5. x = 0.8, 6. x = 1.0

The relation of oi with the oxide ion vacancies is now described b r i e f -

ly. As we reported previously, the partial substitution of Sr2+ for La3+ of
the perovskite-type oxide generates an equivalent amount of oxide ion vacan-
cies at elevated temperatures (16). On cooling in oxygen atmosphere, the
vacancies tend to be occupied with absorbed oxygen. The oxygen absorbed in
this way can be measured from the TPD chromatograms of oxygen. For example,
such chromatograms are shown for Lal-xSrxCoO.4FeO.603-6 in Fig. 4. Obviously
the oxygen desorption is seen to be a trace at x = 0 but increase sharply as
x increases: the desorbed amounts below 1123 K were 4.8 (x = 0.2), 9.4 (0.4),
23.7 (0.6), 51.6 (0.8), and 45.0 (1.0) in u n i t of surface monolayer, respec-
t i v e l y . I t can be shown that these amounts coincide roughly with the nominal
amounts of oxide ion vacancies at elavated temperatures. Therefore, the
sharp increase of oi with increasing x as well as the decrease of oi with
increasing P02 can be explained well in terms of the concentration of oxide
ion vacancies. The modest dependence of ~i on y was f a i r l y consistent with
the result of TPD experiments which showed that the amount of desorbed oxygen
was l i t t l e affected by the B site substitution.

Ionic conduction mechanism

For oxide ion conduction via vacancy mechanism, oi is expressed as

56 Y. TERAOKA, et al. Vol. 23, No. 1

follows. y in Loo.6SFo.4COl.yFey03-8
o i = (Zq)2 Cv Dv / k T [2] 0 0.2 0,4 0,6 0,8 1,0
! ! i ! ! !

where Cv and Dv are the number

of oxide ion vacancies per unit
volume and the diffusion coeffi- 2o
cient of oxide ion vacancies,
r e s p e c t i v e l y , and Zq is the
charge of c a r r i e r , k is Boltz-
mann constant and T is absolute
temperature. Ishigaki et al.
(12) reported that the tempera-
ture dependence of Dv in LaCo03
was expressed by the equation 15 i , , ,
Dv[cm2 s - l ] =
0 0,2 0,4 0,6 0,8 1,0
1.59 x 10-2 exp (Ea / R T) [3] x in LOl_xSFxCOo.8Feo.203-a
Ea = 18 _+ 5 kcal mol-1, FIG. 5
Effects of A and B site substitutions
where R is gas constant. When on the apparent activation energy for
the mole fraction of oxide ion oxide ion conduction in He atmosphere.
vacancies is assumed to be 10%
(8 = 0.3), Cv is derived to be
roughly equal to 5.0 x 1021 10 o
cm-~, and thus ~i can be es-
Oin He
timated as 1 - 10-2 S cm-1 at
1073 K by using Eqs. [2] and
0 in oir
[3]. T h i s estimation coincides
f a i r l y well with the observed oi
shown in Fig. 3.

E
The apparent a c t i v a t i o n i0-]
energy (Ea) for oxide ion condu- O0
ction in He atmosphere is shown colculoted
in Fig. 5 as a function of A or Eg from J*
B site composition. Ea ranged
from 15.5 to 20.7 kcal mol-1,
which was reasonably close to
the reported activation energy
for migration of oxide ion va-
cancies in LaCo03 and LaFe03, 10.2
18 ± 5 k c a l m o l - 1 ( 1 2 , 1 3 ) .
These r e s u l t s not o n l y s u p p o r t
t h a t the o x i d e ion c o n d u c t i o n
occurs v i a a vacancy mechanism,
but a l s o appear to assure t h a t 0,9 i,i 1,3
the f o u r - p r o b e i o n i c dc t e c h -
nique employed in t h i s s t u d y
T-I/lo-3 K-I
gives reliable data of i o n i c
FIG. 6
c o n d u c t i v i t y f o r a mixed conduc-
Applicability of measured ionic conduc-
t o r having a small i o n i c t r a n s -
t i v i t i e s to the rate of oxygen semiperme-
port number.
ation (J*) for LaO.6Sro.4Co03-6.
Vol. 23, No. 1 P E R O V S K I T E - T Y P E OXIDES 57

Relation to oxygen semipermeability

As we reported previously (10), the rate of oxygen semipermeability of
Lal-xSrxCol-yFey03-6 increased as the contents of Sr and Co increased, though
Sr content was more i n f l u e n t i a l . This trend in oxygen semipermeability
agrees well with that in oxide ion conductivity shown in Fig. 3. Figure 6
compares the ai values of LaO.6SrO.4Co03-6 measured in this study with those
calculated from the rate of oxygen semipermeability by assuming the following
equation.

oilS cm-l] = 5.7 x 103 (Jd/T)[log ( p ' / p " ) ] - I [4]

where J is the rate of oxygen semipermeability [cm3(STP) min-1 cm-2], d is

the thickness of the disc [cm], T is temperature [K], and P' and P" are the
oxygen partial pressures of the atmospheres separated by the perovskite-type
oxide membrane, 21 and 0.1 kPa, respectively. The calculated values are seen
to be close to the measured ones. Such a coincidence is reasonable because
the oxygen semipermeability of Lal-xSrxCol-yFey03-6, a s u f f i c i e n t l y high
electronic conductor, is controlled by the ionlc conductivity.

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