Journal of the European Ceramic Society 27 (2007) 4291–4296

Sol–gel synthesis, X-ray photoelectron spectroscopy and electrical

conductivity of Co-doped (La, Sr)(Ga, Mg)O3−δ perovskites
Riccardo Polini a,∗ , Alessia Falsetti a , Enrico Traversa a , Oliver Schäf b , Philippe Knauth b
a Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma Tor Vergata, Via della Ricerca Scientifica, 00133 Roma, Italy
b MADIREL (UMR 6121) Université de Provence, CNRS, Centre Saint Jérôme, F-13397 Marseille Cedex 20, France

Available online 26 March 2007

Abstract
La0.8 Sr0.2 Ga0.8 Mg0.2−x Cox O3−δ (LSGMC) powders containing different amounts of Co (x = 0.05 and 0.085) were prepared by a citrate sol–gel
method. The powders were used to prepare highly phase-pure LSGMC sintered pellets with controlled composition and fractional densities larger
than 95%. For the first time, LSGMC materials were subjected to X-ray photoelectron spectroscopy (XPS) characterization. XPS data confirmed
the presence of the dopants in the material and allowed to identify two different chemical states for Sr2+ and oxygen, both related to the oxygen-
deficient perovskite structure of LSGMC. The conductivity of LSGMC sintered pellets containing different amounts of Co ions in the B sites of the
perovskite lattice was assessed by electrochemical impedance spectroscopy (EIS) in the 250–750 ◦ C temperature range. Conductivity values and
apparent activation energies were in good agreement with previously published data referring to materials with same composition, but prepared
by solid-state route. Therefore, the physicochemical and electrochemical characterization clearly demonstrated the ability of sol–gel methods to
produce high-purity Co-doped LSGM perovskites, which represent promising solid electrolytes for intermediate-temperature SOFCs.
© 2007 Elsevier Ltd. All rights reserved.

Keywords: Powders-chemical preparation; Sol–gel processes; Mixed ionic-electronic conductivity; Perovskites

1. Introduction an ionic conductor due to the appearance of n- or p-type con-

duction. However, it was found that the oxide ion conductivity
Solid oxide fuel cells (SOFCs) offer a highly efficient power was also improved by doping Co for Ga site of LaGaO3 -based
generation system. One of the major requirements for the perovskites,7 although hole conduction was detected at high
development and commercialization of low-cost SOFCs is the oxygen partial pressures.7,11 Yamada et al.12 demonstrated that
reduction of the operating temperature. One of the ways to reach the application of Co-doped LSGM as electrolyte in SOFCs
this aim is the use of solid electrolytes exhibiting superior ionic greatly improves the power density of the cell at intermediate
conductivity at intermediate temperatures (T < 800 ◦ C). Among temperatures.
these ionic conductors, doped LaGaO3 materials show high LSGM materials are usually prepared by time- and
oxide ion conductivity in the 600–800 ◦ C range. The incorpora- energy-consuming solid-state reaction,1,2 although new pow-
tion of divalent cation dopants to form La1−x Srx Ga1−y Mgy O3−δ der production techniques have been used. Aldinger and
(LSGM, where δ = (x + y)/2), gives mobile oxygen vacancies. coworkers13,14 have studied the preparation of LSGM powders
As a consequence, the resulting ionic conductivity of LSGM by the Pechini method, which is a versatile sol–gel method that
at 700 ◦ C is about four times larger than that of conventional proceeds via the formation of a polymeric resin using citric
yttria-stabilized zirconia (YSZ) solid electrolyte.1–3 Following acid and ethylene glycol.15 However, sol–gel methods can give
the initial discovery,1–5 numerous experimental studies have LSGM materials containing small amounts of undesired phases
been carried out on LSGM materials, which also include the such as SrLaGa3 O7 , SrLaGaO4 13 and MgO.16 Majewski et al.14
effect of transition-metal doping.6–11 It is generally believed showed that sintering temperatures as high as 1500 ◦ C were nec-
that doping with a transition-metal cation is undesirable for essary to prepare pure La0.8 Sr0.2 Ga0.8 Mg0.2 O2.8 ceramics by
using mixed oxide route or Pechini method. Schulz and Martin17
reported the sol–gel synthesis of pure La0.8 Sr0.2 Ga0.8 Mg0.2 O2.8
∗ Corresponding author. Tel.: +39 06 7259 4414; fax: +39 06 7259 4328. electrolyte. However, to get a pure perovskite, they performed a
E-mail address: [email protected] (R. Polini). very long (120 h) treatment at 1400 ◦ C of the uniaxially pressed

0955-2219/$ – see front matter © 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jeurceramsoc.2007.02.147
4292 R. Polini et al. / Journal of the European Ceramic Society 27 (2007) 4291–4296

multiphase precursor, i.e. typical conditions of solid-state reac-

tion. Given the promising properties of Co-doped LSGM
(LSGMC) electrolytes for the development of intermediate-
temperature (IT) SOFCs, we continued our previous work
on sol–gel synthesis of dense LSGM ceramics16 and present
the physicochemical and electrical characterization of LSGMC
electrolytes prepared by sol–gel method.

2. Experimental procedure

La0.8 Sr0.2 Ga0.8 Mg0.2−x Cox O3−δ (LSGMC) powders with

two cobalt concentrations (x = 0.05 and 0.085) were synthe-
sized using the following starting materials: La2 O3 (99.9% pure,
Aldrich), SrCO3 (99% pure, Carlo Erba), MgO (99% pure, Carlo
Erba), metallic Co (99.9% pure, Aldrich), and a fresh solution
of standardized Ga(NO3 )3 ·xH2 O (99.9% pure, Aldrich). Before
weighing, MgO and La2 O3 were fired at 1000 ◦ C overnight to Fig. 1. XRD patterns of LSGMC0.05 pellets after 20 h sintering at 1475 ◦ C
decompose carbonate and hydroxide impurities. Stoichiometric and of LSGMC0.085 pellets obtained after 5, 10 and 20 h sintering at the same
amounts of solid powders were dissolved in HNO3 :H2 O = 1:1 temperature.
and then the proper amount of Ga3+ solution was added at room
temperature. Citric acid was added in the molar ratio 2:1 with was calibrated with respect to Au 4f7/2 (BE = 83.8 eV). Binding
respect to the total amount of cations. Heating this solution at energies were calibrated with respect to the C 1s component
80–90 ◦ C under stirring yielded a gel, where the cations were at 285.0 eV, attributable to carbon-based contaminants at the
expected to be statistically distributed in chelate complexes. The sample surface.20 The error in the determination of the binding
formed gel was heated further until solid foam was formed. energies was ±0.2 eV.
The foam was then ground and dried at 200 ◦ C overnight. The Sintered pellets were observed by field emission gun scan-
dried resin was ground, slowly heated (0.5 ◦ C/min) to 450 ◦ C, ning electron microscopy (FEG-SEM, Leo Supra 35) and their
held at this temperature for 2 h and then heated up to 1000 ◦ C chemical composition was assessed by energy dispersive X-ray
at 10 ◦ C/min and held at this temperature for 24 h. This pre- spectroscopy (EDS, Oxford Inca 300). Electrical conductivi-
calcination step was required (i) to decompose all remaining ties were measured by electrochemical impedance spectroscopy
organic residuals and (ii) to form Ga-containing phases thus (EIS) with an EGG 6310 spectrometer between 0.1 and 100 kHz.
avoiding the formation of Ga2 O3 that could decompose to Ga2 O The amplitude of the signal was 20 mV and the electrode mate-
and O2 at high sintering temperatures.18 In fact, following this rial was sputtered platinum.
calcination step (24 h at 1000 ◦ C), both perovskite phase and
small quantities of SrLaGaO4 and SrLaGa3 O7 were formed.19 3. Results and discussion
The powders were then ground in an agate mortar and then uni-
axially pressed at 300 MPa using a 13 mm cylindrical die. The Fig. 1 shows the XRD patterns of the pellets after sintering at
pellets were sintered in air at 1475 ◦ C for 5, 10 or 20 h, with 1475 ◦ C. No secondary phases could be detected in the sintered
a heating rate of 10 ◦ C/min. The density of the sintered pellets LSGMC0.05 . However, in LSGMC0.085 pellets small amounts of
was determined by Archimede’s technique. electrically insulating 214 phase (SrLaGaO4 ) were detectable,
Table 1 summarizes nominal compositions, sintering treat- even after 20 h of sintering.
ments and the density of the pellets. LSGMCx refers to These results were in agreement with previously published
La0.8 Sr0.2 Ga0.8 Mg0.2−x Cox O3−δ materials, where x represents XRD patterns of La0.8 Sr0.2 Ga0.85−x Mg0.15 Cox O3−δ materials
the fraction of cobalt ions that substitute Mg2+ in the B sites synthesized by conventional solid-state route, which showed
of the perovskite. Two different Co concentrations were stud- small amounts of 214 phase in samples containing 10 or 20 mol%
ied (x = 0.05 and 0.085). Phase purity of calcined powders and Co and no secondary phases in LSGMC pellets doped with
of sintered pellets was determined by X-ray diffraction (XRD, 5 mol% Co.21
Philips X’Pert Pro, Cu K␣ radiation) at room temperature. SEM micrographs of LSGMC pellets sintered for 20 h are
In the case of LSGMC0.085 materials, pellets sintered at shown in Fig. 2. Equally dense microstructures were observed
1475 ◦ C for 5, 10 and 20 h were analyzed by X-ray photoelec- also for LSGMC0.085 pellets sintered for 5 or 10 h, thus confirm-
tron spectroscopy (XPS). XPS spectra were acquired using a ing that all samples exhibited a high density and a negligible
Leybold Heraeus LHS10 spectrometer equipped with an EA11 amount of residual porosity.
electron energy analyzer. The excitation source was Al K␣ XPS spectra of La 3d, Sr 3d, Ga 2p, Mg 1s, Co 2p and O
radiation (hν = 1486.6 eV). The analyzer operated in the fixed- 1s regions were analyzed for LSGMC0.085 sintered pellets. The
analyzer transmission (FAT) mode with constant pass energy spectra were very similar for all the samples and Fig. 3 shows
of 50 eV. The binding energy (BE) values were referred to the the results for LSGMC0.085 pellet subjected to 20 h sintering
Fermi level of the electron energy analyzer. The spectrometer (LSGMC0.085 20).
 R. Polini et al. / Journal of the European Ceramic Society 27 (2007) 4291–4296 4293

Table 1
Nominal composition, sintering cycle, and density of sintered pellets
Sample Nominal composition Sintering cycle Density (g/cm3 ) Fractional density (%)

LSGMC0.085 5 1475 ◦ C (5 h) 6.40 95.8

LSGMC0.085 10 La0.8 Sr0.2 Ga0.8 Mg0.115 Co0.085 O3−δ 1475 ◦ C (10 h) 6.37 95.4
LSGMC0.085 20 1475 ◦ C (20 h) 6.43 96.3
LSGMC0.05 La0.80 Sr0.20 Ga0.80 Mg0.15 Co0.05 O3−δ 1475 ◦ C (20 h) 6.22 95.1

The core and satellite peaks of La 3d5/2 and La 3d3/2 were sep- blet feature with the peak energies at 528.9 and 531.6 eV. The
arated by 3.9 eV and the binding energy of the La 3d5/2 core level full widths at half maximum (FWHM) of the two components
was 833.5 eV, a value in good agreement with those reported were 1.6 and 2.6 eV, respectively. The sharper component at
previously for La0.8 Sr0.2 CoO3 .22,23 lower binding energy is typical of O2− ions.24 The nature of
Sr 3d band showed multiple components. A careful fit- the other component at larger binding energy has been stud-
ting procedure allowed identifying four components, namely ied extensively by Imamura et al.31 These authors assigned the
two 3d5/2–3/2 doublets with 1.79 eV splitting between 3d5/2 larger binding energy component (at 531.5 eV) to O2 species that
and 3d3/2 peaks, a value in excellent agreement with literature are molecularly adsorbed in the subsurface regions of oxygen-
data.24,25 The 3d5/2 peaks were at 133.9 and 132.0 eV, respec- deficient perovskite-type compounds during the cooling period
tively. Therefore, these components could not be attributed to after calcination. This adsorbed oxygen is presumably incorpo-
SrCO3 (133.2 eV). The first and most intense 3d5/2 component rated in the material along grain boundaries, because oxygen
(at 133.9 eV) is attributable to Sr2+ in the perovskite lattice, deficiency is not large enough to accommodate a negatively
being its BE comparable to those measured in similar perovskite charged dioxygen molecule.
structures.23,27 The BE of 3d5/2 weaker component (at 132.0 eV) The conductivity in air of LSGMCx materials with x ≤ 0.085
was close to that of SrO1−δ suboxide (132.2 eV, Ref. 28). There- is expected to be mostly ionic at high temperatures with a
fore, we infer that this component could be attributed to Sr2+ transport number of oxide ions larger than 0.8 at T ≥ 600 ◦ C.7
ions surrounded by vacancies in the oxygen-deficient perovskite Furthermore, Ishihara et al.7 showed that the electrical con-
structure. ductivity of LSGMC0.085 at higher temperatures was almost
The XPS spectra for gallium unambiguously confirmed the independent of the oxygen partial pressure. Therefore, it was
Ga3+ state, with a BE value of the Ga 2p3/2 level at 1116.8 eV. decided to carry out the electrical characterization of Co-doped
The BE of the weak Mg 1s core level peak at 1304.2 eV is close LSGM materials in air and at temperatures up to about 800 ◦ C.
to that previously reported for Mg2+ in LSGM by Shkerin et The results of the total electrical conductivity measure-
al.27 The Co 2p3/2 signal gave a distorted peak at 779.9 eV, ments are reported in Fig. 5 in the form of Arrhenius plots.
in good agreement with the BE of Co3+ ions in LaCoO3 and LSGMC0.085 exhibited larger electrical conductivities than
La1−x Cax CoO3 perovskites.23,29 Pure CoO and Co3 O4 exhibit LSGMC0.05 due to the larger cobalt concentration. The total
a 2p3/2 peak centred at 780.4 and 780.1 eV, respectively.20,29 conductivity of LSGMC0.05 and LSGMC0.085 at 615–620 ◦ C,
Therefore, different oxidation states of Co ions could not be dis- i.e. at typical operating temperatures for IT-SOFCs, were 0.024
criminated since binding energies are similar.26 The presence of and 0.057 S cm−1 , respectively. These values were larger than
Co2+ should be assessed by satellite peaks in the 785–788 eV those of yttria-stabilized zirconia (YSZ, 8.1 × 10−3 S cm−1 at
range.26,30 However, due to the low Co concentration (∼2 wt.%) 700 ◦ C)32 and La0.8 Sr0.2 Ga0.8 Mg0.2 O2.8 (0.020–0.043 S cm−1
in LSGMC0.085 and the consequent low intensity of the Co 2p at 600–650 ◦ C).3,7
signal, the lack of satellite peaks in our spectra did not allow to At high temperatures the ionic conductivity, σ ion ,
exclude the presence of divalent cobalt in our sintered materials. is predominant7 and Khorkounov et al.21 showed
Fig. 4 shows the O 1s core level spectrum of the that the ionic conductivities at 700 ◦ C and 900 ◦ C of
LSGMC0.085 20 sintered pellet. The spectrum showed a dou- La0.8 Sr0.2 Ga0.8 Mg0.15 Co0.05 O3−δ sintered pellets prepared by

Fig. 2. SEM micrographs of pellets sintered for 20 h at 1475 ◦ C: (a) LSGMC0.05 and (b) LSGMC0.085 .
4294 R. Polini et al. / Journal of the European Ceramic Society 27 (2007) 4291–4296

Fig. 4. O 1s core level of LSGMC0.085 pellet sintered at 1475 ◦ C for 20 h.

solid-state route were 8 and 20 times larger, respectively, than

the hole conductivity at the same temperatures and 1 bar oxygen
partial pressure (σpo ). In the case of Co-doped LSGM, the total
conductivity, σ tot , can be expressed as a function of σ ion and
σpo 21 :
1/4
σtot = σion + σpo p2 (1)

Our conductivity measurements were performed in air, where

1/4
pO2 = 0.67. Therefore, the ionic to hole conductivity ratios are
expected to be even higher than those given in Ref. 21.
The high temperature activation energies for our LSGMC0.05
and LSGMC0.085 pellets were 0.62 and 0.45 eV, respectively, and
in good agreement with previously published data.7,21,33
Ishihara et al.7 found that the apparent activation
energy for high temperature electrical conductivity of
La0.8 Sr0.2 Ga0.8 Mg0.2−x Cox O3−δ decreased with Co content in
the B sites of the perovskite and was lower than that of
La0.8 Sr0.2 Ga0.8 Mg0.2 O2.8 materials (0.80 eV). Khorkounov et
al.21 also found a similar trend, with activation energies for
ionic conductivities ranging from 0.51 to 0.68 eV. Therefore,
although we did not measure the pO2 dependence of conductiv-
ity, the good agreement of high temperature activation energies
in Fig. 5 with activation energies for ionic conduction published
in the literature confirmed the predominant ionic conductivity
at high temperatures.

Fig. 3. XPS spectra of La 3d5/2 , Sr 3d5/2 , Ga 3p3/2 , Mg 1s, Co 2p3/2 peaks of

LSGMC0.085 pellet sintered at 1475 ◦ C for 20 h.

Fig. 5. Arrhenius plots of electrical conductivity of LSGMC0.05 and

LSGMC0.085 pellets prepared by sol–gel method and sintered at 1475 ◦ C (20 h).
 R. Polini et al. / Journal of the European Ceramic Society 27 (2007) 4291–4296 4295

The Arrhenius plots were linear also in the lower temper- relationships and electrical properties. J. Am. Ceram. Soc., 1998, 81,
ature region, but with significantly lower slopes (Fig. 5). This 2565–2575.
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