April 16, 2009 17:50 00051

Functional Materials Letters

Vol. 2, No. 1 (2009) 33–36
© World Scientific Publishing Company

STRUCTURAL ANALYSIS AND IONIC CONDUCTIVITY AT ROOM

TEMPERATURE OF A Ce-DOPED La0.9 MnO3−δ PEROVSKITE
PREPARED BY THE PECHINI ROUTE

FARIDA BOUREMMAD∗ , ABDERRAHIM BENABBAS,

NEDJMEDDINE BOUNAR and KAMEL RIDA
LIME Laboratory, University of Jijel, BP 98 Jijel, 18000, Algeria
PATRICK ROPA and JEAN-CLAUDE CARRU†
LEMCEL Laboratory, BP 717, Calais, 62228, France

Received 22 December 2008; Revised 21 January 2009

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A Ce-doped La0.9 MnO3−δ sample was prepared by the Pechini route, consisting of a polymerization of citric acid and ethylene
glycol, in order to prepare a phase with oxygen deficiency that can be used in fuel cell applications. To substitute a part of
lanthanum by cerium, we added CeO2 in excess to force it to react and diffuse in the perovskite. The Fourier Transformed
infrared (FTIR) spectrum of the resin at 200◦ C has shown the formation of complex metals form and polymerized form of
ethylene glycol. The X-ray diffraction (XRD) spectrum of the sample, calcined at 900◦ C, has revealed that the sample is mainly
constituted by a deficient rhombohedra perovskite phase. The measurement of the ionic conductivity by complex impedance
at room temperature has given a relatively high value, which opens up an opportunity for solid oxide fuel cell applications.

Keywords: Ceramics; perovskite; sol–gel preparation; ionic conductivity; Rietveld refinement.

Solid oxide fuel cells (SOFCs) are considered as power gen- to ionic radii, expressed by the Goldsmith factor,9 and to
eration devices for the future, as they have demonstrated high ionic charges.10 Oxygen vacancies are created by aliovalent
energy-conversion efficiency. They are under development substitutions on the A site and/or the B site. LaMnO3 pos-
and efforts are made to reduce their operating temperature, sesses orthorhombic GdFeO3 type structure11; the transition
which depends particularly on properties of the electrolyte to the rhombohedral cell is achieved by A cation vacancies,12
material.1,2 Many oxide ionic conductors can exhibit high which create oxygen vacancies but also induce mixed valences
ionic conductivity at low temperature; they find applications Mn3+ /Mn4+ favorable for the electronic conduction. For
in several electrochemical devices, such as SOFCs, oxygen ionic conduction purposes, the electronic contribution must
sensors and membrane reactors for oxidative catalysis.3–5 be minimized; the Mn4+ content is reduced by increasing
It has been proven that the perovskites ABO3 with tran- the average charge of A cations through the incorporation
sition metal on the B site, such as Mn and Co, are potential of Ce4+ , and even these cations are characterized by a low
candidates for SOFC application in the intermediate and low solubility (3%).13
temperature ranges.6 We report here the synthesis of a Ce-doped La0.9 MnO3−δ
A high concentration of mobile charge carriers, i.e. oxide perovskite by the Pechini method, based on polyesterifica-
ion vacancies, and a nearly equal energy of the oxide ion site tion between citric acid and ethylene glycol. The sample
are necessary for high ionic conductivity.7,8 The latter con- was investigated by X-ray diffraction (XRD), Fourier-
dition is verified when only one oxygen site is involved in transformed infrared spectroscopy (FTIR) and scanning
the asymmetric unit of the crystal structure, as in the cases electron microscopy (SEM), and its electrical properties were
of cubic (Pm-3m) and rhombohedral (R-3c) perovskites. The measured by electrochemical impedance spectroscopy (EIS)
stability and the symmetry of perovskite structure are related at room temperature, 293 K.
The Ce-doped La0.9 MnO3−δ oxide was prepared by the
∗bouremmad_farida@[Link] Pechini route, based on polyesterification between citric acid
†carru@[Link] and ethylene glycol.14 We used an excess of Ce (6%) in order

33
 April 16, 2009 17:50 00051

34 F. Bouremmad et al.

to force cerium atoms to be more incorporated in the perovskite used as a solvent for the process of polymerization to form an
structure. The starting materials, La(NO3 )2 · 6H2 O, Ce(NO3 )· intermediate type resin; it inhibits metal ion segregation and
H2 O and Mn(NO3 )2 · 4H2 O, were dissolved in citric acid (CA) achieves a homogeneous precursor in the polymerization of
solution and ethylene glycol (EG) solution according to the citric-acid–metal complexes.16,17
molar ratio, inorganic atoms: CA:EG = [Link]. The obtained FTIR spectra of the gel at 200◦C (Fig. 1) show a broad
sol was heated at 90◦ C under stirring until a clear gel was band around 3460 cm−1, characteristic of the hydroxyl group.
obtained. After that, it was heated at 130◦ C until a spongy dark The band at 1730 cm−1 indicates that inorganic elements were
gel remained, and no sign of precipitation was observed. To coordinated to the carbonyl group16; this is confirmed by the
remove the solvent, the gel was submitted to decomposition at band in 1407 cm−1, which also indicates complexation of inor-
200◦C for 2 h and at 500◦C for 1 h. The obtained resin was then ganic ions (Ce4+ , La3+ and Mn4+ ) mainly with carboxylate
reground and calcined at 800◦C and finally at 900◦ C for 5 h. ions in the dry gel. The band at 1624 cm−1 is attributed to
Several techniques were employed for the phase charac- the asymmetric stretching mode and that at 1395 cm−1 to the
terization at different states. FTIR spectroscopy measurements symmetric stretching mode of a carbonyl group resonance.
were carried out with a SHIMADZU FTIR 84005 apparatus The band at 1180 cm−1 is due to the C–C–O structure of ethy-
for the gel and the calcined sample. FTIR spectra were scanned lene glycol in the polymerization process.18,19 For the sample
between 4000 and 400 cm−1 . The XRD experiments were at 900◦C, we note that all bands corresponding to the organic
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performed on a D8 Advance Bruker AXS diffractometer with phases have disappeared. We also note that a band at 600 cm−1
CuKα radiation equipped with a curved graphite monochro- was observed; it can be assigned to the metal oxide group.
mator. Data were collected in the 2θ range of 20–120◦, with Figure 2 shows the XRD pattern of the sample calcined
a step size of 0.02◦ and a count time of 12 s per step. The at 900◦C. We recognize the perovskite phase in the majority
XRD pattern was inspected using the Brucker AXS software (JCPDS card No. 32-0484) and CeO2 (JCPDS card No. 43-
package EVA to identify the present phases in the sample. 1002) with the fluorite structure type as a minor phase which
Data were further analyzed by the Rietveld method, using the is stoichiometric and has not any deficiency in oxygen; conse-
Brucker AXS software package TOPAS 2.115 to obtain struc- quently it does not present ionic conductivity. A preliminary
tural details of these phases. An SEM image was recorded at
room temperature on a PHILIPS XL 30 apparatus.
For the impedance spectroscopy measurements, powder
was ground and pressed into a pellet (11 mm diameter and
about 1 mm thickness). The pellet was sintered at 900◦ C for
5 h in air, and then metallized and placed between two elec-
trodes. Impedance measurements were done at room temper-
ature, 293 K; a Hewlett-Packard 4284A apparatus was used in
a frequency range from 20 Hz to 1 MHz, with an oscillating
voltage of 100 mV.
Figure 1 shows the different steps of the perovskite for-
mation by means of FTIR analysis. In the Pechini method,
citric acid is used to chelate metal ions and ethylene glycol is

Fig. 2. XRD pattern of the sample calcined at 900◦ C.

Transmittance (%)

(110)p
(104)p Perovskite (p): 91.61%
CeO2 (c): 8.39 %

200˚C (024)p
(214)p

(022)c (331)c
(202)p (208)p
(012)p (311)c (128)p
(220)p
500˚ C (404)p (324)p
(048)p
(111)c (238)p
(122) (312)p (226)p
900˚C (416)p

500 1000 1500 2000 2500 3000 3500 4000

-1
cm

Fig. 1. FTIR spectra of the sample at different temperatures. Fig. 3. Rietvelt plot: observed–calculated and difference profile.
 April 16, 2009 17:50 00051

Structural Analysis and Ionic Conductivity of a Ce-Doped La0.9 MnO3−δ Perovskite 35

Table 1. Crystallographic data for (La,Ce)0.92 MnO2.91 .

Atoms x y z Ratio Beq (Å) Interatomic distances

(La, Ce) 0 0 0.25 0.92 (2) 1.062 Mn–O 1.9599(4) × 6

Mn 0 0 0 1 0.652 La–O 2.5001 × 3
O 0.45329 (6) 0 0.25 0.9630 (5) 0.762 2.7497 × 6
3.015 × 3

Space group R-3c (No. 167) Cell Volume: 352.011(1) Å3

Cell parameters: a = 5.51548(8) Å; c = 13.3616(2) Å
R p : 5.77% Rwp : 7.66% GOF: 1.43 R-Bragg = 1.925

full-pattern decomposition using the Lebail method confirms

the rhombohedral symmetry of the perovskite structure.
Figure 3 shows the difference between observed and
calculated diffraction profiles in the Rietveld refinement. A
pseudo-Voigt function and shifted Chebyshev polynomials
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were particularly used to describe the peak shape and back-

ground levels, respectively. At the final stages, the occupan-
cies of the atoms were alternately refined, which attested to
the presence of vacancies on both the A and oxygen sites,
whereas the Mn site was fully occupied due to the nearly equal
electronic density of La3+ and Ce4+ cations. It was not pos-
sible to refine their individual contributions to the A site. The
final structural parameters for the perovskite are summarized Fig. 4. SEM micrograph of the sample calcined at 900◦ C.
in Table 1. A comparison of the crystal cell parameters is
made with those of pure La-deficient perovskites: the data for 5
Z"(Ohm)

La0.9 MnO3 20 (ICSD code 50044) and La0.93 MnO3 21 (ICSD

code 75216) respectively of a = 5.5266 Å, c = 13.3547 Å and 4

a = 5.529 Å, c = 13.363 Å, show, as expected, that both

3
the a and c parameters increase with La3+ and consequently
Mn3+ content. Moreover, the c/a ratio also increases owing 2 20 Hz
to the geometry of octahedral around Mn3+ cations. The 10 6 Hz
cell parameters of our perovskite phase (La, Ce)0.92 MnO3 1

(a = 5.5155 Å and c = 13.3616 Å) indicate particularly a

decrease of the parameter a which can be related to both the 0
28 30 32 34 36 38
higher charge and the smaller size of the Ce4+ cation com- Z' (Ohm)
pared to the La3+ one. Furthermore, c/a has increased, a sign
Fig. 5. Impedance spectra of the sample at room temperature.
of the Mn3+ content increasing, which confirms our viewpoint
and shows that our purpose has been attained.
Figure 4 shows the SEM micrograph of the Ce-doped (20 Hz–1 MHz), not all of the three arcs were observed for
La0.9 MnO3−δ sample after heating at 900◦C for 5 h; we can our sample; Fig. 5 shows the typical Nyquist representation
see homogeneous particles with an average size of ∼0.5 µm. for the sample at room temperature. We have obtained two
Complex impedance spectroscopy is a technique for arcs, and the magnitude order of the capacitance associated
the characterization of the electrical behavior of electrolytes: with the high frequency arc is in the nF range, which is typical
impedance of an ionic conductor contains the contributions of of boundary grain response, while the capacitance of the low
bulk-grain, grain-boundaries and electrode–electrolyte inter- frequency arc is in the µF range, typical of electrode factors.
faces at high, middle and low frequencies.1 Impedance spectra We have determined the bulk resistance from the left intercept
are represented in the Nyquist form, where the imaginary part of the first semicircle with the real axis; the obtained value is
Z  is plotted against the real part Z  . Usually, for the different about 27 .
phenomena cited above, three successive arcs are observed The conductivity σ has been calculated from the relation
in the Nyquist representation associated with an RC subcir- σ = L/(R · S), where L is the thickness and S the area of
cuit. Due to the limited frequency range of the equipment the pellet; its value is 3 · 10−3 S · cm−1 at room temperature
 April 16, 2009 17:50 00051

36 F. Bouremmad et al.

(293 K). This is a relatively high value compared with those 5. J. B. Goodenough, Nature 404, 821 (2000).
obtained for some other oxides, generally measured at high 6. A. Yan et al., Appl. Catal. B: Environ. 76, 320 (2007).
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