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Thermodynamic data of Ba

0.6
Sr
0.4
Co
0.8
Fe
0.2
O
3d
SOFC cathode material
A. Botea-Petcu
a
, S. Tanasescu
a,
*, V. Varazashvili
b
, N. Lejava
b
, T. Machaladze
b
,
M. Khundadze
b
, F. Maxim
a
, F. Teodorescu
a
, J. Martynczuk
c
, Z. Yng
d
, L.J. Gauckler
d
a
Institute of Physical Chemistry Ilie Murgulescu, Romanian Academy, Bucharest, Romania
b
Ivan Javakhishvili Tbilisi State University, R. Agladze Institute of Inorganic Chemistry and Electrochemistry, Tbilisi, Georgia
c
Electron Microscopy ETH Zurich, ETH Zurich, Zurich, Switzerland
d
Nonmetallic Inorganic Materials, Department of Materials, ETH Zurich, Zurich, Switzerland
A R T I C L E I N F O
Article history:
Received 16 December 2013
Received in revised form 15 April 2014
Accepted 1 June 2014
Available online 4 June 2014
Keywords:
A. Oxides
C. Electrochemical measurements
C. Thermogravimetric analysis (TGA)
D. Thermodynamic properties
D. Defects
A B S T R A C T
The compound Ba
0.6
Sr
0.4
Co
0.8
Fe
0.2
O
3d
with perovskite structure has been studied focusing mainly on
the thermodynamic stability in correlation to the change in the oxygen stoichiometry. The
thermochemical behavior has been investigated from room temperature to 1300K by thermal
gravimetry and differential thermal analysis in air and by calorimetry in scanning mode in Argon. The
temperature dependence of enthalpy (DH
T
298
) in the temperature range of 300900K was measured by
drop calorimetry. Thermodynamic properties represented by the relative partial molar free energies,
enthalpies and entropies of oxygen dissolution in the perovskite phase, as well as the equilibriumpartial
pressures of oxygen have been obtained in the temperature range of 8231273K using solid electrolyte
electrochemical cells (EMF). The inuence of the oxygen stoichiometry on the thermodynamic properties
was examined using a coulometric titration technique coupled with EMF measurements. The results are
discussed based on the strong correlation between the energetic parameters and the charge
compensation of the material system.
2014 Elsevier Ltd. All rights reserved.
1. Introduction
Searching for new materials for intermediate-temperature solid
oxide fuel cells (IT-SOFCs), the mixed ionic-electronic conducting
(MIEC) perovskite oxides (Ba,Sr)(Co,Fe)O
3d
(BSCF) have received
great attention [18]. These oxides may show a high electronic
conductivity due to the mixed valence states of the transitional
metals and high oxide ion conductivity related to the high oxygen
vacancyconcentration. Theproperties of the BSCFcompoundscanbe
tailored by varying the Ba:Sr and Co:Fe ratios. The signicant oxygen
non-stoichiometry deviations (0.3 < d < 0.8 at 873 < T < 1173 K)
exhibited by the Ba
x
Sr
1x
Co
y
Fe
1y
O
3d
perovskites, together with
the variation of the structural characteristics are depending on
temperature and oxygen partial pressure [913] leading to
substantial variations in the electrochemical activity of electrodes.
As a SOFC cathode, the long-term stability of such a highly
defective material under the operating conditions of an IT-SOFC is
crucial. Most of the quaternary BSCF compounds exhibit cubic
symmetry at 1273K in air. Some of the BSCF compositions undergo
a cubic to hexagonal transition at low temperatures as polymorphs
of hexagonal symmetry in the BSCF system are expected regarding
the symmetries of the end members in this system [14,15].
Especially under reducing conditions (<10
5
atm) the thermal
treatment showed decomposition through a complex series of
phase transitions due to ordering [5,6]. Although the knowledge of
the fundamental solid state chemistry in the BSCF materials,
including the relation between defect structure and thermody-
namic stability has increased during the years, the role of the
energetic parameters as driving forces leading to materials with
the greatest stability during operation is still needed.
In the BSCF series, the composition Ba
0.5
Sr
0.5
Co
0.8
Fe
0.2
O
3d
(BSCF5582) has been of particular interest as it has a good oxygen
permeation [1,2,16,17], and low non-ohmic losses as IT-SOFC
cathodes [3,1820]. However, even for this composition, the
degradation of the permeability and of the oxygen ion conduction
associated with the formation of less symmetrical non-cubic
phases at 9731173 K was already reported [1,15,21,22]. By using
transmission electron microscopy, Emov [23] reported in the
intermediate temperature range below 1123 K the decomposition
of cubic BSCF5582 into a mixture of phases including a lamellar-
shaped Ba
x
Sr
1x
Co
2y
Fe
y
O
5d
complex oxide in addition to
* Corresponding author at: Institute of Physical Chemistry "Ilie Murgulescu",
Splaiul Independentei 202, P.O.Box. 12-194, 060021 Bucharest, Romania.
Tel.: +40 21 3167912/72 2789838; fax: +40 21 3121147.
E-mail addresses: stanasescu2004@yahoo.com, speranta.tanasescu@gmail.com,
stanasescu@icf.ro (S. Tanasescu).
http://dx.doi.org/10.1016/j.materresbull.2014.06.002
0025-5408/ 2014 Elsevier Ltd. All rights reserved.
Materials Research Bulletin 57 (2014) 184189
Contents lists available at ScienceDirect
Materials Research Bulletin
j our na l homepage: www. el sevi er . com/ l ocat e/ mat r esbu
hexagonal perovskite Ba
0.6
Sr
0.4
CoO
3d
. Searching for the phase
stability and the decomposition pathway of cubic
Ba
0.5
Sr
0.5
Co
0.8
Fe
0.2
O
3d
, P. Mller et al. [24,25] reported that the
crystallization of the hexagonal phase is limited to temperatures
below 1103 K and the growth of plate-like regions with trigonal
crystal structure was detected up to 1173 K annealing. The
formation of secondary phases will have a negative impact on
oxygen-ion conduction, by increasing the lattice stress and
decreasing the oxygen vacancies mobility.
Compared with BSCF5582composition, the BSCF6482 based
cathode material has been reported by Zhao et al. [4] to exhibit
better cell performance due to the relatively higher electrical
conductivity at intermediate temperatures (8731073 K). The
values of activation energy for the conductivity found by Wei
et al. [8] and Yang et al. [15] are smaller for the composition with
x = 0.6 comparatively with the corresponding values obtained for
x = 0.5. Nevertheless, comparatively with BSCF5582, very little
work was performed on the BSCF6482.
When varying the Ba/Sr ratio in Ba
x
Sr
1x
Co
0.8
Fe
0.2
O
3d
(from
x = 0.2 to 0.8) a maximum in the partial molar free energy is
obtained in the temperature range from 800 to 900 K for 50 mol%
Ba, indicating the compositions with x = 0.5 and y = 0.2 to have the
highest oxide ionic conductivity [26] and at 900 K, the thermody-
namic data suggest an increase of the oxygen vacancies
concentration correlated with higher oxygen conductivity for
the composition with 60 mol% Ba, consistent with the analysis by
Zhao et al. [4]. To our best knowledge, no other thermodynamic
characterization of compounds in the BSCF system is available.
In the present paper, the thermodynamic properties of the
Ba
0.6
Sr
0.4
Co
0.8
Fe
0.2
O
3d
(BSCF6482) material is characterized from
room temperature to 1300 K and the correlation between the
thermodynamic parameters and the change in the oxygen non-
stoichiometry is given.
2. Experimental
The powder specimens of Ba
0.6
Sr
0.4
Co
0.8
Fe
0.2
O
3d
were syn-
thesized by solid state reaction method which was previously
described in detail [15,26]. According to the X-ray diffraction
(XRD), furnace quenched powders of Ba
0.6
Sr
0.4
Co
0.8
Fe
0.2
O
3d
calcined at 1273 K in air exhibit pure cubic perovskite structure
[15,26].
The morphology of the samples was analyzed by scanning
electron microscopy (SEM) using a FEI Quanta 3D equipment. In
order to evidence the surface features of the particles the scanning
was performed at low acceleration voltage of the electrons
(maximum 5 kV) using the backscatter detector (BSED) in beam
deceleration mode.
The solid-oxide electrolyte galvanic cells method was employed
to obtain the thermodynamic properties of the samples. As shown
in previous papers [2729], the thermodynamic stability limits of
the ABO
3d
perovskite-type oxides are conveniently situated
within the range of oxygen chemical potentials, that can be
measured using electrochemical cells containing 12.84 wt.% yttria-
stabilized zirconia solid electrolyte and an iron-wstite reference
electrode. The design of the apparatus, as well as the theoretical
and experimental considerations related to the applied method
has been previously described [30]. Measurements were per-
formed in vacuum at a residual gas pressure of 10
7
atm. The
electromotive force (EMF) was measured with a Keithley 2000
Multimeter, at 50 K intervals between 823 K and 1273K, each time
waiting until equilibrium conditions were obtained. Equilibrium
conditions were achieved when values for increasing and
decreasing temperatures agreed within 1 or 2 mV in the EMF. By
using the experimental values of the electromotive force of the cell
and knowing the free energy change of the reference electrode
[3134], the values of the relative partial molar free energies,
enthalpies and entropies, as well as the equilibrium partial
pressures of oxygen were obtained according to the known
relationships [28]. The overall uncertainty due to the temperature
and potential measurement (taking into account the overall
uncertainty of a single measurement and also the quoted accuracy
of the voltmeter) was 1.5mV. This was equivalent to 0.579 kJ
mol
1
for the free energy change of the cell. Considering the
uncertainty of 0.523 kJ mol
1
in the thermodynamic data for the
iron-wstite reference [3134], the overall data accuracy was
estimated to be 1.6kJ mol
1
. For the enthalpies the errors were
0.45 kJ mol
1
and for the entropies 1.1 J mol
1
K
1
. Errors due to
the data taken from the literature are not included in these values
because of the unavailability of reliable standard deviations.
By solid-state coulometric titration [28,30] the precise change
of the oxygen stoichiometry was obtained. The titrations were
performed in situ at 1123 K by using a Bi-PAD Tacussel Potentiostat.
After titration and equilibration, by changing the temperature
under the open-circuit condition, the variation of EMF with
temperature was again recorded.
In order to further evaluate the results regarding the partial
molar thermodynamic data of selected compositions, the thermal
behavior was investigated by differential thermal analysis (DTA),
thermal gravimetry (TG), and drop calorimetry. The DTA/TG
measurements on powder specimens were performed as a
function of temperature in air in the temperature range 298
1300 K by using the DTA/TG equipment (F. Paulk, I. Paulik, L. Erday
type Q-1500D). Two series of measurements were performed
with a scanning rate of 10 K/min. The heat effects related to the
anomalies evidenced on the DTA curves in air were then
investigated by DTA measurements in Argon by using the high
temperature calorimeter HT-1500 Setaram [35]. The measure-
ments were performed in Argon at a pressure of about 1.1atm, in
the temperature range of 2981300K and with a scanning rate of
200 K/h.
The enthalpy of the BSCF samples was investigated in the
temperature range 300900 K using the Calvet-type microcalo-
rimeter Setaram in the drop regime [36]. To avoid the quenching
effect at calorimetric experiments, the drop method cold ! hot
was used. The heat capture which happens at the dropping process
of the sample from initial room temperature into the block of hot
furnace is taken into account. To avoid this problem a special
supplementary device was applied to the Calvet calorimeter, which
provides the optimal condition for dropping experiment [36].
The measuring error is 11.5% for a minimal sample amount of less
than 5 mg.
3. Results and discussion
By using the experimental values of the electromotive force of
the cell, the thermodynamic data represented by the relative
partial molar free energies (DG

O
2
), enthalpies (DH

O
2
) and entropies
(DS

O
2
) of the oxygen dissolution in the perovskite phase, as well as
the equilibrium partial pressures of oxygen have been calculated
according to the known relationships [28,30]. The partial molar
free energies (DG

O
2
) and the corresponding logp
O
2
for the
BSCF6482 sample are shown in Fig. 1. DG

O
2
strongly increases
with increasing temperature until 923 K, then continues to slowly
increase to 1023 K. After 1023 K DG

O
2
decreases with increasing
temperature to 1273 K. Even though in the temperature interval of
9231273 K a smaller dependence on temperature of DG

O
2
is
noted, the variation of DG

O
2
with temperature above 923 K is not
monotonous, some anomalies being observed at 1023 and 1173 K.
The same trend holds for the logp
O
2
variation (Fig. 1).
In a previous study [26] we showed that at temperatures above
923 K, DG

O
2
of BSCF6482 is higher thanDG

O
2
of BSCF5582. In Fig. 2
A. Botea-Petcu et al. / Materials Research Bulletin 57 (2014) 184189 185
t-
h-
e
DG

O
2
values of BSCF6482 and BSCF5582 compositions at temper-
atures between 923 and 1223 K are plotted on the same diagram
for comparison. Due to the high values of the partial molar energies
of the BSCF6482 composition, the oxygen vacancy concentration is
expected to be high in this sample. A higher oxygen vacancy
concentration means more carriers for oxygen transport; this
results in a higher oxygen ionic conductivity for BSCF6482 sample
above 923 K compared to BSCF5582, which is in agreement with
the analysis performed by Zhao et al. [4]. 60% Ba stabilizes the
perovskite-structure with cubic symmetry more effectively and
thus contributes indirectly to the good electrochemical perfor-
mance evidenced for this composition.
In Fig. 3 the SEM analysis of the BSCF6482 sample is shown.
Particles with round tip branches and dimensions around 12 mm
are formed. The sample presents particles with peculiar nano-
structured features at the surface suggesting good oxygen
conductivity through the oxygen vacancies [37,38]. This observa-
tion is in good agreement to the thermodynamic data which
indicate a high concentration of oxygen vacancies for the sample
BSCF6482 in the intermediate temperature range.
Further clarication could be achieved by determining the DH

O
2
and DS

O
2
values in particular temperature ranges in which the
partial molar free energies are linear functions of temperature,
namely 9731073K and 10731223 K for x = 0.5; 9231023 K and
10231173 K for x = 0.6 (Fig. 2). The increasing Ba concentration has
a distinct effect on the enthalpy and entropy suggesting a change of
the predominant defects concentration for the compounds with
both the Ba content and the temperature. Thus, at temperatures
lower than the points of transitions (Fig. 4), DH

O
2
and DS

O
2
values
strongly decrease (with 240 kJ mol
1
and 250 J mol
1
K
1
respectively) from x = 0.5 to x = 0.6. The decrease of the partial
molar enthalpy and entropy values suggests the increase of the
binding energy of oxygen and an increase of order in the oxygen
sublattice of the perovskite-type structure, respectively. Above the
points of transitions, an increase of 12 kJ mol
1
for DH
O
2
and a
decrease of only 8 J mol
1
K
1
for DS

O
2
are obtained for the
sample with x = 0.6 (Fig. 4).
In Fig. 5(a) the mass change of BSCF6482 during two
consequent heating from room temperature to 1300 K is shown.
Above 700 K, BSCF6482 shows considerable loss of oxygen,
consistent with earlier results [8,39]. The thermal induced oxygen
losses can lead to the increase of oxygen vacancies in agreement
with the behavior of the DG

O
2
variation at the moderate
temperature range of 823923 K (see Fig. 2). The maximal value
of weight change is 1.6%. This behavior is also measured by the
drop calorimetry method (Fig. 6). The temperature dependences of
enthalpy DH
T
298
for the temperature range 300900 K are divided
in two parts: the rst in the temperature interval (300700 K),
where the weight loss is negligible. The second part (T > 700 K)
corresponds to the temperatures where loss of oxygen is large.
Endothermic effects in air are revealed for the composition
1300 1200 1100 1000 900 800
-350
-300
-250
-200
-150
-100
8 9 10 11 12
-25
-20
-15
-10
-5
10
4
(T/K)
-1
l
o
g

(
p
O
2
/
a
t
m
)
G
O
2

G
O
2

/

k
J

m
o
l
-
1
T/K
log p
O
2
Fig. 1. Variation of DG

O2
and logp
O2
with temperature.
1200 1100 1000 900
-155
-150
-145
-140
-135
-130
-125
-120
BSCF 5582
BSCF 6482

G
O
2
/

k
J

m
o
l
-
1
T / K
Fig. 2. Variation of DG

O2
with temperature and Ba content - linear t in the
selected temperature ranges: 9731073 K and 10731223 K for x = 0.5; 923
1023 K and 10231173 K for x = 0.6.
Fig. 3. SEM micrographs of the sample BSCF6482 acquired in Beam deceleration mode using BSED.
186 A. Botea-Petcu et al. / Materials Research Bulletin 57 (2014) 184189
B-
a-
0.-
6-
S-
r
0-
.4-
C-
o-
0.-
8-
F-
e-
0.-
2-
O-
3-
d
at
a-
bout 650700 K and two other anomalies after 1100 K (Fig. 5(b)).
The second heating was carried out after the rst series of DTA-TG
measurements and after cooling the sample in the furnace in air.
Due to the reversibility of the oxygen loss, the initial weight of the
sample at the beginning of the second heating has reached the
initial values within a variation of 0.2%.
The heat effects related to the anomalies evidenced on the DTA
curves in air were then evaluated by calorimetric measurements in
scanning mode in Argon (Fig. 7). The temperature intervals of these
anomalies in Argon are generally shifted to higher temperatures
comparatively with that obtained in air, namely they are 793
831 K (Fig. 7(a)); 10531063K (Fig. 7(b)); and 11451165 K
(Fig. 7(c)) with the heat of transitions of about 4.1 J/g, 4.8 and
11.9 J/g, respectively. In agreement with the results obtained from
EMF measurements, the rst two anomalies can be assigned to
structural transformation related to the charge compensation of
the material system. With increasing temperature the appearance
of some secondary phases which are - with further heating to
above 1063 K - incorporated into the BSCF lattice was noted in our
and other literature in situ X-ray diffraction data [6,15,40]. The last
anomaly is due to nal structural transformation to cubic form,
evidenced by XRD performed on this composition showing the
cubic perovskite phase at 1273 K in earlier work [15].
According to the DG

O
2
data, the compounds will show different
oxygen stoichiometries at different temperatures. Increasing
temperature leads to an increase of the oxygen nonstoichiometry
and concomitant reduction of the transition metal cations on the
Co/Fe-sites as required by charge compensation. Since the reduced
cations tend to be larger in size than the oxidized ones, their
presence will favor formation of the cubic perovskite structure at
high temperature.
In order to further evaluate the previous results, the variation of
the thermodynamic data of oxygen dissolution was analyzed at the
same relative stoichiometry change of Dd = 0.01. In Figs. 8 and 9,
two sets of data obtained before and after the isothermal titration
experiments are plotted. After titration, the DG

O
2
and logp
O
2
values
are decreasing. The release of oxygen resulted in the decrease of
DG

O
2
values which is indicative for the decrease of oxygen vacancy
concentration. It was noted that the DG

O
2
and logp
O
2
shifted to
higher values with increasing temperature, the higher deviation
with the stoichiometry change of the DG

O
2
and logp
O
2
values being
obtained at 1123 K. With increasing temperature the oxygen
stoichiometry decreases, which will result in the formation of
oxygen vacancies. The obtained results suggest that the energy of
vacancy formation decreases with increasing nonstoichiometry
Fig. 5. (a) The weight loss and (b) DTA signals of BSCF6482 as a function of temperature in air (TG1, DTG1 and DTA1 rst heating; TG2, DTG2 and DTA2 second heating).
900 800 700 600 500 400 300
0
50
100
150
200
250
300
350

H
T
2
9
8
.
1
5
/
J
g
-
1
T/K
Fig. 6. Enthalphy of BSCF6482 obtained by isothermal drop calorimetry in the
temperature interval 300900 K.
0.60 0.55 0.50
-200
-150
-100
-50
0
50
100
-0.05
0.00
0.05
0.10
0.15
0.20
0.25

S
O
2
/

k
J

m
o
l
-
1
K
-
1
H
O
2
(T<T
tr
)
H
O
2
(T > T
tr
)

H
O
2
/

k
J

m
o
l
-
1
Ba content (x, mol)
S
O
2
(T<T
tr
)
S
O
2
(T > T
tr
)
Fig. 4. DH

O2
and DS

O2
as a function of Ba content (x) in the temperature
ranges before and after temperature of transitions (T
tr
)dened as 1073 K for
BSCF5582 and 1023 K for BSCF6482.
A. Botea-Petcu et al. / Materials Research Bulletin 57 (2014) 184189 187
and conrm the strong effect of the charge compensation of the
material system on the energetic parameters.
4. Conclusions
The energetic parameters obtained by a couple of measure-
ments (EMF, TG, DSC, Drop Calorimetry) allow for the correlation of
the thermodynamic stability with the defect structure in particular
temperature ranges.
The thermodynamic data of oxygen dissolution have a strong
dependence on the temperature, and show signicant variations
with respect to the oxygen stoichiometry change. These may
explain the different behaviors in the different temperature
regimes. The oxygen vacancy order also shows contribution to
the observed phenomena. At the same temperature, the values of
the thermodynamic data of oxygen dissolution are decreasing with
the decreasing stoichiometry.
The results help to explain the high oxide ionic conductivity
reported for x = 0.6. The current research attests the inherent phase
instability of the investigated BSCF composition during heating at
temperatures lower than 1023 K. The temperature of some
structural transformations related to the charge compensation
of the material system was evidenced.
Acknowledgments
The SNSF (Swiss National Science Foundation) nancial support
by the Scopes JRP Project IZ73Z0_128185/1/2009 is greatly
acknowledged. The authors acknowledge the Romanian Academy,
as well as EU (ERDF) and Romanian Government support for
acquisition of the research infrastructure under Project INFRANA-
NOCHEM/20092010. One of the authors (F.M.) gratefully
acknowledges the support of the Romanian National Authority
for Scientic Research, CNCSUEFISCDI by the grant PN-II-RU-TE-
2011-3-0160.
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-240
-220
-200
-180
-160
-140
-120
BSCF 6482 before titration
BSCF 6482 after titration

G
O
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m
o
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Fig. 8. Variation of DG

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-0.01
0.00
BSCF 6482 before titration
BSCF 6482 after titration
l
o
g
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O
2
/
a
t
m
)

1
0 4
(
T
/
K
)
-
1
Fig. 9. Variation of logp
O2
with temperature and oxygen stoichiometry change
(Dd = 0.01) for BSCF6482.
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