Available online at www.sciencedirect.

com

CERAMICS
INTERNATIONAL

Ceramics International ] (]]]]) ]]]]]]

www.elsevier.com/locate/ceramint

Synthesis of La0.9Sr0.1Ga0.8Mg0.2O3
electrolyte via ethylene glycol route

and its characterizations for IT-SOFC
Raghvendra, Rajesh Kumar Singh, Prabhakar Singhn
Department of Physics, Indian Institute of Technology (Banaras Hindu University) Varanasi 221005, India
Received 24 November 2013; received in revised form 12 December 2013; accepted 12 December 2013

Abstract
Strontium and magnesium doped lanthanum gallate (La0.9Sr0.1Ga0.8Mg0.2O3
), known as LSGM, was rst prepared via ethylene glycol
method. This route of preparation showed improved electrical conductivity, better surface area and high density. X-ray diffraction patterns of
LSGM sintered at different temperatures indicated that pure LSGM phase was formed after sintering at 1400 1C. X-ray Rietveld renement
conrmed the formation of pure perovskite orthorhombic phase of the LSGM. The sintered sample showed 99% relative density. Scanning
electron microscopic study of LSGM also depicted fairly densed grain morphology. X-ray photoelectron spectroscopy measurement conrmed
the stability of the sintered sample in air and the existence of constituent elements in their characteristic valence states. A surface without porosity
was observed in BET measurement. Average thermal expansion coefcient was found to be 9.78  10
6/1C in the measured temperature range
(RT1000 1C). The frequency dependent electrical conductivity of the sample was measured in the temperature range 400800 1C. Total
electrical conductivity of the LSGM pellet was found to be 0.056 S cm
1 at 800 1C.
& 2013 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
Keywords: C. Electrical conductivity; Ethylene glycol route; LSGM; IT-SOFC

1. Introduction
A solid oxide fuel cell (SOFC) is an energy conversion
device that generates electricity and heat by electrochemically
combining a gaseous fuel (hydrogen) and an oxidant gas
(oxygen from air) through electrodes across an ion conducting
solid electrolyte [1,2]. An electrolyte should be a good ionic
conductor for obtaining the high power density in the SOFCs.
Also, the electrolyte must be stable both in fuel and air
atmospheres and should have very low electronic conductivity
to prevent leakage current [3]. A few well established solid
electrolyte materials for SOFCs are; yttria stabilized zirconia
(YSZ) [4,5], Gadolinia/Samaria Doped Ceria (GDC/SDC)
[6,7], and stabilized Bi2O3 [8]. A typical SOFC, which uses
YSZ as the electrolyte requires high operating temperatures
( 1000 1C) in order to obtain high ionic conductivity. The
high operating temperature required for YSZ could cause
technological problems such as mechanical instability, reduced
lifetime and undesirable reactions among the cell components
n

Corresponding author. Tel.: 91 542 6701916, fax: 91 542 2368428.

E-mail address: psingh.app@iitbhu.ac.in (P. Singh).

[9]. At lower temperatures ( o 800 1C), the ionic conductivity

of GDC and Bi2O3 electrolytes are higher compared to YSZ.
Although their ionic conductivities are good enough, a few
major problems like the material instability (in bismuth oxide)
and the mixed conduction (in doped ceria) under fuel gas
conditions are difcult to overcome [10]. In 1994, Ishihara
et al. [11] proposed a new material based on doped LaGaO3
(La0.9Sr0.1Ga0.8Mg0.2O3
; LSGM) with the perovskite structure as a new promising electrolyte material for SOFC
application. This showed high ionic conductivity and better
stability both in fuel and air atmospheres at moderate
temperature, which makes it one of the most promising solid
electrolyte for intermediate temperature solid oxide fuel cell
(ITSOFC) [12,13]. The LSGM material exhibits a high oxide
ion conduction over a broad range of oxygen partial pressures
(11022 atm) and therefore, it is a promising candidate to
replace YSZ as an electrolyte in SOFCs operating at relatively
low temperatures (500800 1C) [14]. In LSGM, secondary
phases are frequently observed, which causes a decrease in its
ionic conductivity [1518]. However, both the phase-purity
and the microstructure of LSGM materials depend on synthesis
procedure and processing. In order to obtain pure LSGM

0272-8842/$ - see front matter & 2013 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
http://dx.doi.org/10.1016/j.ceramint.2013.12.056
Please cite this article as: Raghvendra, et al., Synthesis of La0.9Sr0.1Ga0.8Mg0.2O3
electrolyte via ethylene glycol route and its characterizations for IT-SOFC,
Ceramics International (2014), http://dx.doi.org/10.1016/j.ceramint.2013.12.056

Raghvendra et al. / Ceramics International ] (]]]]) ]]]]]]

powders and improved electrical performance, several synthesis routes have been adopted [19] such as conventional solid
state [20], Pechini [21], spray pyrolysis [22], combustion
method [23], wet chemical synthesis [24], polymerization
route [25] etc. Generally, solgel, glycine-nitrate combustion
and solid state reaction were opt frequently to prepare the
electrolyte and electrode powders. For solgel and glycinenitrate combustion, the starting materials can be mixed
homogeneously at molecular or at atomic levels in the
solution, and ne powders with few secondary phases can be
obtained [19,26,27]. Huang et al. [28] synthesized La0.9Sr0.1Ga0.8Mg0.2O2.85 powder using solgel method with ammonium hydroxide as complexing agent and they obtained pure
perovskite phase at 1350 1C. The glycine-nitrate combustion
was selected to prepare La0.8Sr0.2Ga0.85Mg0.15O3
by Cong
et al. [27]. The resulting material showed the existence of
impure phase of LaSrGa3O7 in the samples after sintering at
1400 1C. When the temperature was further increased to
1550 1C, the impurity phases were found to disappear and
powders with pure phase could be obtained. Chae et al. [29]
discussed the properties of cobalt doped LSGM and synthesized La0.9Sr0.1Ga0.8Mg0.2O2.85 by means of carbonate coprecipitation using ammonium carbonate as precipitant. In
their study, pure phase of LSGM was produced by calcination
of the precursor at 1400 1C for 6 h. Chen et al. [30] reported a
new method called low temperature hydrothermal urea precipitation process to synthesize La0.8Sr0.2Ga0.8Mg0.2O2.8 and
the conductivity obtained was 0.056 S cm
1 at 800 1C.
Besides the above mentioned methods, ethylene glycol
route, which is generally used for obtaining metallic particles
and preparing phosphor materials [31], could also be used to
synthesize oxide powders. The basis of this method is the
precipitation of solid materials while heating with sufcient
precursors in a multivalent and high-boiling point alcohol such
as ethylene glycol (EG). Here the alcohol acts as a stabilizer,
limits the particle growth and prohibits the agglomeration of
particles [32]. Materials, obtained from this method, show
homogenous phase composition, narrow particle distribution
and high specic surface area. Also, the morphology could be
controlled by changing the reaction time and the concentration
of the precursor [33]. In this study, we report the synthesis of
perovskite type La0.9Sr0.1Ga0.8Mg0.2O3
(LSGM) powders
via ethylene glycol method without using any protective
compound (surfactant) for the rst time. We also investigated
the structure, surface morphology, elemental connement,
textural behavior, thermal expansion and electrical properties
employing X-ray Rietveld analysis, scanning electron microscopy, X-ray photoelectron spectroscopy, BET surface area
measurement, dialatometry and impedance spectroscopy techniques, respectively.
2. Experimental
2.1. Synthesis
A stoichiometric amount of lanthanum (III) oxide (La2O3,
99.9%, Alfa Aesar), strontium (II) oxide (SrO, 99.99%, Alfa

Aesar), gallium (III) oxide (Ga2O3, 99.99%, Alfa Aesar),

magnesium (II) oxide (MgO, 99.9%, Alfa Aesar) were
dissolved in concentrated nitric acid and the solution was
heated at 80 1C in double distilled water at least ve times in
order to remove the excess acid. The solution was kept inside a
conical ask under constant magnetic stirring. 100 ml of
ethylene glycol (EG) and 2.0 g of urea were added to it and
placed under constant stirring for 1 h for uniform mixing. The
reaction mixture was heated at 150 1C for 3 h under reux
condition until the precipitation was completed. The reaction
was easily followed through its distinctive color changes. The
solution becomes light yellow, indicating the reduction of
glycol. After 5 h of reaction, the solution became light brown.
The precipitate of as-synthesized material so obtained was
washed three to four times by centrifugation in ethanol to
remove the excess of EG. Hydrolysis of urea (NH2CONH2)
produces NH4OH, which acts as precipitating agent. Decomposition temperature of urea in water medium (120 1C) is
lower than that in gas/solid phase (190 1C) and it produces
NH4OH and CO2. NH4OH molecules precipitate La3 , Sr2 ,
Ga3 and Mg2 ions to their corresponding oxides or/and
hydroxides. The oxide powders were dried for 12 h at 100 1C
in a hot air oven. During the reaction, when nucleation starts,
the EG molecules (solvent) surround the smaller particles to
form a chemical bond between EG and surface of particle and
thus, particle growth is hindered. This helps in reduction of
agglomeration of smaller particles and also the surface of the
particles is functionalized. Thus, this synthesis route produces
ne powders. The prepared composition was characterized
using various techniques. The details of the characterization
techniques are mentioned in the subsequent section.
2.2. Characterizations
The crystal structure of the LSGM was identied by Rigaku
Miniex II desktop powder X-ray diffractometer (XRD) with Ni
ltered Cu-K (1.5405 ) radiation at 30 kV and 20 mA.
Patterns were recorded over the angular range 15r2/1r90
with a step size of 2 0.021. For phase identication, the
experimental XRD patterns were analyzed by Rietveld renement. After polishing and thermal etching, the microstructures of
the sintered sample were examined by scanning electron microscopy. SEM image of polished surface of the pellet were recorded
with help of Quanta 200 FESEM. Density measurements were
carried out using the Archimedes principle. A balance system
(Model AX, Mettler-Toledo, Giessen, Germany) was used for
determining the density. Relative densities were calculated by
measuring the sintered pellet density divided by theoretical
density as derived from the lattice parameters. The specic
surface area of calcined powders was estimated by BET method
through Micromeritics (ASAP 2020) Accelerated Surface Area
and Porosimetry System using adsorptiondesorption isotherms
of nitrogen. Prior to BET analysis, the powders were degassed
under vacuum for 6 h at 300 1C. Dilatometry of the sample was
performed in air using a dilatometer DIL 402 PC (NETZSCH,
UK) from room temperature to 1000 1C. AC impedance spectroscopy technique is well suited for the measurement of electrical

Please cite this article as: Raghvendra, et al., Synthesis of La0.9Sr0.1Ga0.8Mg0.2O3
electrolyte via ethylene glycol route and its characterizations for IT-SOFC,
Ceramics International (2014), http://dx.doi.org/10.1016/j.ceramint.2013.12.056

Raghvendra et al. / Ceramics International ] (]]]]) ]]]]]]

conductivities of solid electrolyte materials. Platinum paint was

used for electrodes on both sides of the sintered LSGM pellets
for the conductivity measurement. Pt-coated pellet was red/
baked at 900 1C to obtain good adhesion between electrolyte and
electrodes. The impedance data were recorded with the help of
Novocontrol impedance analyser. Measurement was carried out
in dry air in the temperature range 400800 1C and in the
frequency range 10
2107 Hz.

3. Results and discussion

3.1. XRD
The development of LSGM phase was studied by recording
the XRD patterns of the system calcined at various temperatures. The phase evolution of LSGM is shown in the XRD
patterns of Fig. 1. The sample, heated at 1100 1C (for 12 h),
contains small amounts of impurity phases like LaSrGa3O7,
LaSrGaO4 and La4Ga2O9 along with the main LSGM phase.
Secondary phases LaSrGa3O7 (ICDD 45-0637), LaSrGaO4
(ICDD 80-1806) and La4Ga2O9 (ICDD 53-1108) became more
apparent in the sample calcined at 1200 1C (6 h). This was
possibly due to the metastable or thermodynamically stable
conditions of the secondary phases [16,17]. The above
impurity phases usually exist along grainboundaries during
the synthesis of LSGM and are of low conducting materials
compared to LSGM. In order to avoid these impurities formed
at 1200 1C, calcination temperature was increased from
1200 1C to 1300 1C and it was observed that these secondary
phases considerably disappeared. Fig. 1 also shows that the
LSGM system, sintered at 1350 1C for 6 h, contains almost no
impurity phase. Tas et al. [21] showed that LSGM powders,
which were synthesized by Pechini method, contained 45 wt
% of LaSrGa3O7/LaSrGaO4 secondary phases after calcination
at 1400 1C for 8 h. Therefore, the ethylene glycol synthesis

route could be a good method for synthesis of LSGM. More

important, this method avoids impurities and eliminates the
requirement of higher calcinations temperature. The LSGM
sample was further sintered at 1400 1C for 6 h to obtain pure
phase. A detailed Rietveld renement was performed using the
XRD data of sintered (at 1400 1C) LSGM powder and is
shown in Fig. 2. The structure renement of the sample was
carried out using Fullprof software. The peak proles were
modeled using Pseudo-Voigt function and background was
described in terms of a six coefcient polynomial. The Rwp
(weighted-pattern factor) and goodness-of-t parameters were
used as numerical criterion of the quality of t of calculated to
experimental diffraction data. Goodenough and Feng [12]
reported that the La0.9Sr0.1Ga0.8Mg0.2O2.85 phase was cubic
perovskite, while Ishihara et al. [11] have reported an
orthorhombic structure for this material. In this study, the
powder patterns were indexed using the orthorhombic cell and
Rietveld renement was carried out on this basis. The results
of Rietveld full pattern renement are given in Table 1. The
atomic model which gave the best t to the data was
orthorhombic, space group Pnma (no. 62), with rened cell
dimensions a 5.4912(4) , b 7.7728(2) and c 5.5229
(5) . Drennan et al. [34] also rened the LSGM using
perovskite orthorhombic phase (Pnma) and found similar
results.

Fig. 2. X-ray Rietveld renement pattern of the LSGM sintered at 1400 1C.
Here Yobs, Ycal, Yobs-Ycal and Bragg position represent the experimental
data, calculated data, the difference of experimental and calculated data and
Bragg0 s positions, respectively. Inset represents the orthorhombic polyhedra of
this system.

Table 1
Parameters obtained by the Rietveld renement of the XRD data of the LSGM.

Fig. 1. X-ray diffraction pattern of LSGM at different calcination temperatures. The symbols , ,
and & represent LSGM, LaSrGaO4, LaSrGa3O7
and La4Ga2O9 phases, respectively.

Atoms

Wyckoff positions

La/Sr
Ga/Mg
O1
O2

4c
4b
4c
8d

0.0146(2)
0
0.4960(16)
0.3726 (22)

0.25
0
0.25
0.0342(12)

0.0037(4)
0.5

0.0689(22)
0.2427(24)

S.G. orthorhombic (Pnma), lattice parameters a 5.4912(4) , b 7.7728

(2) , c 5.5229(5) ; V 235.73(6) 3, Rp 12.2%, Rwp 15.6%, Rexp
13.6, and 2 4.31.

Please cite this article as: Raghvendra, et al., Synthesis of La0.9Sr0.1Ga0.8Mg0.2O3
electrolyte via ethylene glycol route and its characterizations for IT-SOFC,
Ceramics International (2014), http://dx.doi.org/10.1016/j.ceramint.2013.12.056

Raghvendra et al. / Ceramics International ] (]]]]) ]]]]]]

spectrum of Ga 2p clearly suggests the presence of Ga 3 state

of Ga, with a binding energy value of the Ga 2p level at
 1116 eV. A weak binding energy peak of magnesium
(Mg 1s) was found at  1303 eV which corroborates with
earlier reported values [39]. The oxygen O 1s broad spectrum,
observed at  530 eV, shows the binding energy peak,
which may be ascribed to the lattice oxygen species and
molecularly adsorbed O2 species. A very weak C 1s peak
arises (at  285 eV) due to carbon contaminants present at the
surface of the sample as shown in the carbon XPS spectrum.
Thus, it is found that sintered sample is stable in air and the
constituent elements are found to exist in their characteristic
valence states.
Fig. 3. SEM image of the polished surface of LSGM system sintered
at 1400 1C.

3.2. Density and scanning electron microscopy

The density of the pellet measured by using Archimedes
principle was found to be  6.59 (g-cm
3) which shows 99%
to the theoretical density. In literature, it was found that the
density value of LSGM electrolyte prepared by Pechini
method was  85% of its theoretical value although the
sample was sintered at 1400 1C for 8 h [33]. In another work,
5.87 (g-cm
3) density was obtained after the calcination of the
pellet at 1400 1C for 32 h by using regenerative solgel
method [35]. These results show the effectiveness of the EG
method compared to other synthesis techniques. Fig. 3 shows
the SEM images of LSGM electrolyte sintered at 1400 1C for
6 h for polished surface. The average grain size was found to
be 68 mm from the SEM micrograph. The average grain size
was found to have lower value than that mentioned in earlier
work [36]. The SEM image also shows very compact grains
having almost no porosity. This also conrms formation of
highly densed sample.
3.3. XPS study
XPS spectra of La 3d, Sr 3d, Ga 2p, Mg 1s and O 1s regions
were analyzed for LSGM sintered powders. Fig. 4 shows the
XPS spectra of conned elements of LSGM. La, Sr, Ga, Mg
and O elements are observed in the system when the binding
energy is below 1350 eV. The XPS spectrum of La 3d states
are found to be split and a clear doublet structure is visible
(peaks at  836 and  852 eV). It is well-known that the La 3d
states, in the XPS spectra, are split not only due to a spinorbit
interaction into two lines 3d5/2 and 3d3/2, but in addition, each
line splits due to a transfer of an electron from oxygen ligands
to the La 4f (initially empty) states [37]. The core and satellite
peaks of La 3d5/2 are found to be separated and the binding
energy of the La 3d5/2 core level was observed to be
approximately 836 eV. This value is in agreement with those
reported earlier for LSGM [38]. From XPS spectrum of Sr 3d,
it can be seen that Sr 3d states show a broad peak (  135 eV),
which might be consisting of 3d5/23/2 doublet. The XPS

3.4. BET surface area measurement

SOFC electrolytes should possess high specic surface area
with very less porosity to produce optimum power density.
Fig. 5 shows an adsorptiondesorption (sorption) curve of the
LSGM. Brunauer, Emmett and Teller (BET), proposed an
equation to describe specic surface area [40]. The BET
equation is
 
1
c
1 p
1

;
1

po =p
1
m po
m c
where p and po are the equilibrium and the saturation pressure
of adsorbates at the temperature of adsorption, is the
adsorbed gas quantity (in volume units), and m is the
monolayer adsorbed
gas quantity. C is the BET constant with



EL
, here E1 is the heat of adsorption for the rst
c exp E1RT
layer, and EL is that for the second and higher layers. In Fig. 5,
the lower part (below relative pressure 0.8) of adsorption was
used for measurement of specic surface area, whereas the
entire range of adsorptiondesorption isotherm is used for pore
analysis. From this gure, it can be seen that the sorption
isotherm depicts type IV hysteresis loop, i.e., the adsorption
and desorption isotherms do not coincide over a certain region
of external pressures. This (type IV) isotherm is typical for
mesoporous (pore size 250 nm) adsorbents [41]. The surface
area of LSGM system was obtained as about 5.19 m2/g from
the BET measurement. Table 2 presents a comparative study of
surface area of LSGM obtained from various synthesis routes.
3.5. Dialatometry
Fig. 6 shows the thermal expansion curve of LSGM sample
in the temperature range 251000 1C. The thermal expansion
coefcient (TEC) is an important characteristic for the application of SOFCs. The physical thermal expansion coefcient ()
can be determined from the slope of this relative length
change curve at a given temperature (T) by the following
equation:
dLo
T  T
Lo

where Lo is the initial length of the sample. The average TEC

of the LSGM pellet, synthesized by the EG synthesis route was

Please cite this article as: Raghvendra, et al., Synthesis of La0.9Sr0.1Ga0.8Mg0.2O3
electrolyte via ethylene glycol route and its characterizations for IT-SOFC,
Ceramics International (2014), http://dx.doi.org/10.1016/j.ceramint.2013.12.056

Raghvendra et al. / Ceramics International ] (]]]]) ]]]]]]

Fig. 4. XPS spectra of constituent elements of LSGM.

like lanthanum manganite, LSM-YSZ composite cathode, the

TEC values are reported as  11  10
6/1C, 10.5  10
6/1C,
respectively [1,43]. Moreover, for interconnect material like
LaCrO3 the TEC value is reported as  9.5  10
6 K
1 [45].
This indicates that the measured TEC value for LSGM,
obtained in present work, is compatible with the TEC values
of anode, cathode and interconnect materials for SOFC.
3.6. AC impedance analysis

Fig. 5. BET surface area sorption isotherm for LSGM.

found to be 9.78  10
6/1C. This value of TEC corroborates

with the earlier reported values for LSGM [12,26,42]. TEC
values for the anode materials like Ni/YSZ cermet and
strontium titanate have been reported as 12.3  10
6/1C and
10.8  10
6 K
1, respectively [43,44]. For cathode materials

High ionic conductivity of LSGM is strongly dependant to

the oxygen vacancy concentration in the material. In the
present system, oxygen vacancies are generated due to the
substitution of Sr2 and Mg2 ion in La3 and Ga3 lattice
sites, respectively as
LaGaO3

00

SrO MgO Sr0La Mg0Ga 2O

o Vo
2

3
2

Thus it is required to maintain the Sr and Mg concentration without destroying the homogeneity of the system [15].
In Fig. 7, we present the Nyquist (ColeCole) impedance plot

Please cite this article as: Raghvendra, et al., Synthesis of La0.9Sr0.1Ga0.8Mg0.2O3
electrolyte via ethylene glycol route and its characterizations for IT-SOFC,
Ceramics International (2014), http://dx.doi.org/10.1016/j.ceramint.2013.12.056

Raghvendra et al. / Ceramics International ] (]]]]) ]]]]]]

Table 2
Properties of LSGM powders prepared by various synthesis routes.
Methods

Particle size (nm)

BET surface area (m2/g)

Density at 1400 1C sintering for 6 h (g/cm3)

References

Solid state
Solgel
Pechini
Ethylene glycol

 50
 10
 150
 120

5.0
92.0
4.5
5.19

6.18
5.19
6.34
6.59

Ref. [24]
Ref. [24]
Ref. [24]
This study

Fig. 6. Thermal expansion coefcient curve of LSGM.

Fig. 7. ColeCole impedance plot of LSGM in the temperature range

500800 1C. Inset showing ColeCole plot of LSGM at 750 1C along with
its electrical equivalent circuit.

for the LSGM at a few selected temperatures. In polycrystalline

ceramic materials, the conductivity relaxation occurred due to
grain, grainboundary and electrode-specimen contributions. Therefore, the impedance spectra consist of grain (bulk), grainboundary
and ceramicelectrode interface contributions. In present investigation, the impedance analysis has been performed in the intermediate temperature range i.e. between 400 and 800 1C. In Fig. 7,
it can be seen that the Nyquist impedance plot consists of two
depressed semicircles and an arc within the measured frequency
range. The high-frequency region depressed semicircle corresponds
to the grain resistance (Rg) and the semicircle in the middlefrequency region represents the resistance of a grainboundary (Rgb)
response. The depressed arc in the lowest frequency regime may be

attributed to the ceramicelectrode interface resistance (Re). For

well separated grain, grainboundary and electrode relaxation
processes, a complete semicircle, corresponding to each process,
is observed. In this case, the equivalent circuit can be replaced by a
parallel combination of respective resistance and capacitance
connected in series. When these three relaxation processes are
not well separated and the obtained semicircles are suppressed, the
capacitances in the equivalent circuit can be replaced with a
constant phase element (CPE) [43]. Moreover, a CPE is needed
also when there is a distortion introduced by local inhomogeneities,
e.g., secondary phases, pores, local charge inhomogeneity, and
variations in composition [18,46,47]. The present LSGM specimen
is a polycrystalline material and may contained inhomogeneity;
therefore, depressed semi-circular arcs were obtained. A CPE was
added to the equivalent circuit mode instead of a capacitor as
shown in the inset of Fig. 7. In the equivalent circuit, CPE1, CPE2
and CPE3 correspond to Cg, Cgb and Ce, respectively. As
temperature increases, grain and grainboundary resistances were
found to decrease, which can be observed by reducing size of the
semicircles. At higher temperatures above 700 1C, the semicircles
were almost disappearing and curved line behavior was observed,
which represents electrode-specimen contribution. The grain and
grainboundary resistances were calculated from the intercepts of
the semicircular arcs on the real part of the impedance axis (x-axis).
We have calculated Rg and Rgb for LSGM at each measured
temperature. The total resistance, Rt, of the sample will be the sum
of Rg and Rgb (excluding the specimen-electrode contribution).
Based on the impedance data and the geometric dimension of the
LSGM pellet, the total electrical conductivity was calculated as per
formula.
1 1
4
st  ;
Rt s
where l is the sample thickness, s is the sample area of the Ptcoated face of the sample. Fig. 8 represents the Arrhenius plot of
total conductivity for the LSGM electrolyte. In this gure, the
temperature dependent conductivity shows straight line behavior in
the entire measured temperature range. Thus the temperature
dependence of the total conductivity of LSGM electrolyte can be
described by the Arrhenius equation,


st T so exp
E a =kT
5
where so, Ea, k and T are the pre-exponential factor, activation
energy, Boltzmann constant and absolute temperature, respectively.
The activation energy was calculated and found to be 0.86 eV in
the entire temperature range. The measured activation energy well
agreed with the previously reported values [37]. The total
conductivity of the LSGM system was obtained as  0.056 S

Please cite this article as: Raghvendra, et al., Synthesis of La0.9Sr0.1Ga0.8Mg0.2O3
electrolyte via ethylene glycol route and its characterizations for IT-SOFC,
Ceramics International (2014), http://dx.doi.org/10.1016/j.ceramint.2013.12.056

Raghvendra et al. / Ceramics International ] (]]]]) ]]]]]]

produce ne powders of the pure LSGM system at relatively

low calcination temperature.

Acknowledgment

Fig. 8. Arrhenius representation of total conductivity for LSGM.

Table 3
Ionic conductivity of LSGM samples prepared by various synthesis routes.
Synthesis method Electrolyte composition

Solid-state
Glycine-nitrate
Carbonatecoprecipitation
Solgel method
Hydrothermal
urea-precipitation
process
Cellulose
templating method
Ethylene glycol

Conductivity
at 800 1C
(S cm
1)

Data
references

0.08
La0.9Sr0.1Ga0.8Mg0.2O3

La0.8Sr0.2Ga0.85Mg0.15O3
0.06
La0.9Sr0.1Ga0.8Mg0.2O2.85
0.045

[20]
[27]
[29]

La0.9Sr0.1Ga0.8Mg0.2O2.85
La0.8Sr0.2Ga0.8Mg0.2O2.8

0.11
0.056

[28]
[30]

La0.8Sr0.2Ga0.83Mg0.17O2.815 0.042

[25]

La0.9Sr0.1Ga0.8Mg0.2O2.85

This study

0.056

cm
1 at 800 1C. The total conductivity was found to be somewhat

lower than the best reported by other authors [17], but it fairly
exceeds the one reported for a LSGM prepared by other chemical
synthesis route and with the same relative density [12,29,25] as
shown in Table 3.
4. Conclusions
La0.9Sr0.1Ga0.8Mg0.2O3
powders have been synthesized
via simple ethylene glycol method in which a relatively low
calcination temperature is needed. The single phase LSGM by
this method was obtained at relatively lower temperature in
comparison to other synthesis techniques. A very high density
( 99%) was achieved after sintering at 1400 1C for 6 h owing
to higher specic surface area. The XPS spectra showed that
constituents of LSGM are assigned to their characteristic
valance state. Thermal expansion coefcient value for LSGM
is found to be compatible with the TEC values of the other
components of SOFC. The total ionic conductivity of the
LSGM was found to be 0.056 S cm
1 at 800 1C. The
activation energy for the conduction process is found to be
0.86 eV. LSGM powders prepared by this method (ethylene
glycol) possess high purity, ne particle size, and better ionic
conductivity. Thus, in comparison to other synthesis routes,
glycol method proves to be a promising synthesis route to

This study was supported by DST-SERC, New Delhi, India

through its Project no. SR/FTP/ETA-0005/2010. We are
thankful to O.P. Pandey and A. Maheshwari for performing
the TEC and electrical measurements, respectively. We
acknowledge to A.S.K. Sinha for providing XPS and BET
surface area measurement facility. We acknowledge also to P.
K. Panda for English language editing. One of the authors,
Raghvendra is thankful to MHRD for providing Teaching
Assistantship.

References
[1] N.Q. Minh, Ceramic fuel cells, J. Am. Ceram. Soc. 76 (1993) 563588.
[2] B.C.H. Steele, A. Heinzel, Materials for fuel-cell technologies, Nature
414 (2001) 345352;
S.C. Singhal, Advances in solid oxide fuel cell technology, Solid State
Ion. 135 (2000) 305313.
[3] V.V. Kharton, F.M.B. Marques, A. Atkinson, Transport properties of
solid oxide electrolyte ceramics: a brief review, Solid State Ion. 174
(2004) 135149.
[4] M. Han, X. Tang, H. Yin, S. Peng, Fabrication, microstructure and
properties of a YSZ electrolyte for SOFCs, J. Power Sources 165 (2007)
757763.
[5] Z. Wang, R. Hui, N. Bogdanovic, Z. Tang, S. Yick, Y. Xie, et al., Plasma
spray synthesis of ultra-ne YSZ powder, J. Power Sources 170 (2007)
145149.
[6] R.K. Lenka, T. Mahata, P.K. Sinha, A.K. Tyagi, Combustion synthesis of
gadolinia-doped ceria using glycine and urea fuels, J. Alloys Compd. 466
(2008) 326329.
[7] D.-S. Kim, P.-S. Cho, J.-H. Lee, D.-Y. Kim, S.B. Lee, Improvement of
grain-boundary conduction in gadolinia-doped ceria via post-sintering
heat treatment, Solid State Ion. 177 (2006) 21252128.
[8] Q. Zhen, G.M. Kale, G. Shi, R. Li, W. He, J. Liu, Processing of dense
nanocrystalline Bi2O3Y2O3 solid electrolyte, Solid State Ion. 176 (2005)
27272733.
[9] A.V. Joshi, J.J. Stephan, D.M. Taylor, S. Elengovan, Solid electrolyte
materials, devices and applications, J. Electroceram. 13 (2004) 619625.
[10] T. Karaca, T.G. Altncekic, M.F. Oksuzomer, Synthesis of nanocrystalline samarium-doped CeO2 (SDC) powders as a solid electrolyte by using
a simple solvo-thermal route, Ceram. Int. 36 (2010) 11011107.
[11] T. Ishihara, H. Matsuda, Y. Takita, Doped LaGaO3 perovskite type oxide
as a new oxide ionic conductor, J. Am. Ceram. Soc. 116 (1994)
38013803.
[12] M. Feng, J.B. Goodenough, A superior oxide-ion electrolyte, Eur. J. Solid
State Inorg. Chem. 31 (1994) 663669.
[13] K. Huang, R.S. Tichy, J.B. Goodenough, Superior perovskite oxide-ion
conductor; strontium- and magnesium-doped LaGaO3: I, phase relationships and electrical properties, J. Am. Ceram. Soc. 81 (1998) 25652575.
[14] P.N. Huang, A. Petric, Superior oxygen ion conductivity of lanthanum
gallate doped with strontium and magnesium, J. Electrochem. Soc. 143
(1996) 16441648.
[15] P. Majewski, M. Rozumek, C.A. Tas, F. Aldinger, Processing of (La,Sr)
(Ga,Mg)O3 solid electrolyte, J. Electroceram. 8 (2002) 6573.
[16] E. Djurado, M. Labeau, Second phases in doped lanthanum gallate
perovskites, J. Eur. Ceram. Soc. 18 (1998) 13971404.
[17] S. Li, B. Bergman, Doping effect on secondary phases, microstructure
and electrical conductivities of LaGaO3 based perovskites, J. Eur. Ceram.
Soc. 29 (2009) 11391146.

Please cite this article as: Raghvendra, et al., Synthesis of La0.9Sr0.1Ga0.8Mg0.2O3
electrolyte via ethylene glycol route and its characterizations for IT-SOFC,
Ceramics International (2014), http://dx.doi.org/10.1016/j.ceramint.2013.12.056

Raghvendra et al. / Ceramics International ] (]]]]) ]]]]]]

[18] Y.-C. Wu, M.-Z. Lee, Properties and microstructural analysis of

La1
xSrxGa1
yMgyO3
solid electrolyte ceramic, Ceram. Int. 39 (2013)
93319341.
[19] R. Polini, A. Pamio, E. Traversa, Effect of synthetic route on sintering
behaviour, phase purity and conductivity of Sr- and Mg-doped LaGaO3
perovskites, J. Eur. Ceram. Soc. 24 (2004) 13651370.
[20] M. Li, Y. Zhang, M. An, Z. L, X. Huang, J. Xiao, B. Wei, X. Zhu,
W. Su, Synthesis and characterization of La0.9Sr0.1Ga0.8Mg0.2O3

intermediate temperature electrolyte using conventional solid state reaction, J. Power Sources 218 (2012) 233236.
[21] A.C. Tas, P.J. Majewski, F. Aldinger, Chemical preparation of pure and
strontium- and/or magnesium-doped lanthanum gallate powders, J. Am.
Ceram. Soc. 83 (2000) 29542960.
[22] D.S. Jung, H.Y. Koo, H.C. Jang, J.H. Kim, Y.H. Cho, J.-H. Lee, et al.,
Firing characteristics of La0.8Sr0.2Ga0.80Mg0.2O3
electrolyte powders
prepared by spray pyrolysis, J. Alloys Compd. 487 (2009) 693697.
[23] M. Shi, et al., Synthesis and characterization of La0.85Sr0.15Ga0.8Mg0.2O2.825 by glycine combustion method and EDTA combustion
method, Powder Technol. 204 (2010) 188193.
[24] K. Huang, J.B. Goodenough, Wet chemical synthesis of Sr- and Mgdoped LaGaO3, a perovskite-type oxide-ion conductor, J. Solid State
Chem. 136 (1998) 274283.
[25] Y. Zhai, C. Ye, F. Xia, J. Xiao, L. Dai, Y. Yang, et al., Preparation of
La0.8Sr0.2Ga0.83Mg0.17O2.815 powders by microwave induced polyvinyl
alcohol solution polymerization, J. Power Sources 162 (2006) 146150;
Vedat Sarboga, Hasan zdemir, M.A. Faruk kszmer, J. Eur. Ceram.
Soc. 33 (2013) 14351446.
[26] J.W. Stevenson, T.R. Armstrong, L.R. Pederson, J. Li, C.A. Lewinsohn,
S. Baskaran, Effect of A-site cation nonstoichiometric on the properties of
doped lanthanum gallate, Solid State Ion. 571 (1998) 113115.
[27] L.G. Cong, T.M. He, Y. Ji, P.F. Guan, Y.L. Huang, W.H. Su, Synthesis
and characterization of IT-electrolyte with perovskite structure
La0.8Sr0.2Ga0.85Mg0.15O3
by glycine-nitrate combustion method, J.
Alloys Compd. 348 (2003) 325331.
[28] K.Q. Huang, M. Feng, J.B. Goodenough, Solgel synthesis of a new
oxide-ion conductor Sr-doped and Mg-doped LaGaO3 perovskite, J. Am.
Ceram. Soc. 79 (1996) 11001104.
[29] N.S. Chae, K.S. Park, Y.S. Yoon, I.S. Yoo, J.S. Kim, H.H. Yoon, Sr- and
Mg-doped LaGaO3 powder synthesis by carbonate coprecipitation,
Colloids Surf. A 313314 (2008) 154157.
[30] T.Y. Chen, K.Z. Fung, Synthesis and densication of oxygen-conducting
La0.8Sr0.2Ga0.8Mg0.2O2.8 nanopowder prepared from a low temperature
hydrothermal urea precipitation process, J. Eur. Ceram. Soc. 28 (2008)
803810.
[31] S.H. Ng, dos D.I. Santos, S.Y. Chew, D. Wexler, J. Wang, S.X. Dou, H.
K. Liu, Polyol-mediated synthesis of ultrane tin oxide nanoparticles for
reversible Li-ion storage, Electrochem. Commun. 9 (2007) 915919.

[32] A.K. Parchur, R.S. Ningthoujam, Preparation and structure renement of

Eu3 doped CaMoO4 nanoparticles, Dalton Trans. 40 (2011) 75907594.
[33] C. Ho, J.C. Yu, T. Kwong, A.C. Mak, S. Lai, Morphology controllable
synthesis of mesoporous CeO2 nano- and microstructures, Chem. Mater.
17 (2005) 45144522.
[34] J. Drennan, V. Zelizk, D. Hay, F.T. Ciacchi, S. Rajendran, S.P.S. Badwal,
Characterisation, conductivity and mechanical properties of the oxygenion conductor La0.9Sr0.1Ga0.8Mg0.2O3
, J. Mater. Chem. 7 (1997)
7983.
[35] B. Rambabu, S. Ghosh, W. Zhao, H. Jena, Innovative processing of dense
LSGM electrolytes for IT-SOFC0 s, J. Power Sources 159 (2006) 2128.
[36] V. Sarboga, H. zdemir, M.A.F. kszmer, Cellulose templating
method for the preparation of La0.8Sr0.2Ga0.83Mg0.17O2.815 (LSGM) solid
oxide electrolyte, J. Eur. Ceram. Soc. 33 (2013) 14351446.
[37] P. Datta, P. Majewski, F. Aldinger, Study of strontium- and magnesiumdoped lanthanum gallate solid electrolyte surface by X-ray photoelectron
spectroscopy, Mater. Res. Bull. 43 (2008) 18.
[38] B. Liu, L. Tang, Y. Zhang, Preparation and characterization of
La0.9Sr0.1Ga0.8Mg0.2O3
thin lm on the porous cathode for SOFC,
Int. J. Hydrogen Energy 34 (2009) 440445.
[39] S.N. Shkerin, M.V. Kuznetsov, N.A. Kalashnikova, X-ray photoelectron
spectroscopy of the surface of solid electrolyte La0.88Sr0.12Ga0.82Mg0.18O3
,
Russ. J. Electrochem. 39 (2003) 591599.
[40] S. Brunauer, P.H. Emmett, E. Teller, Adsorption of gases in multimolecular layers, J. Am. Chem. Soc. 60 (1938) 309319.
[41] S. Lowell, et al., Characterization of Porous Solids and Powders: Surface
Area, Pore Size and Density, Springer Science Business Media, New
York, 2004.
[42] T. Ishihara, M. Honda, T. Shibayama, H. Furutani, Y. Takita, An
intermediate temperature solid oxide fuel cell utilizing superior oxide
ion conducting electrolyte, doubly doped LaGaO3 perovskite, Ionics 4
(1998) 395402.
[43] F. Tietz, Thermal expansion of SOFC materials, Ionics 5 (1999) 129139.
[44] O.A. Marina, N.L. Caneld, J.W. Stevenson, Thermal, electrical, and
electrocatalytical properties of lanthanum-doped strontium titanate, Solid
State Ion. 149 (2002) 2128.
[45] W.Z. Zhu, S.C. Deevi, Development of interconnect materials for solid
oxide fuel cells, Mater. Sci. Eng. A 348 (2003) 227243.
[46] J.R. Macdonald, Impedance Spectroscopy: Emphasizing Solid Materials
and Systems, Wiley Co, New York, 1987.
[47] J.E. Bauerle, Study of solid electrolyte polarization by a complex
admittance method, J. Phys. Chem. Solids 30 (1969) 26572670.

Please cite this article as: Raghvendra, et al., Synthesis of La0.9Sr0.1Ga0.8Mg0.2O3
electrolyte via ethylene glycol route and its characterizations for IT-SOFC,
Ceramics International (2014), http://dx.doi.org/10.1016/j.ceramint.2013.12.056