Solid State Ionics 201 (2011) 3541

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Solid State Ionics

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / s s i

Characterization of Ln0.5M0.5FeO3 (Ln = La, Nd, Sm; M = Ba, Sr) perovskites as SOFC cathodes
A. Ecija a,, K. Vidal a, A. Larraaga a, A. Martnez-Amesti a, L. Ortega-San-Martn b, M.I. Arriortua a,
a b

Universidad del Pas Vasco/Euskal Herriko Unibertsitatea (UPV/EHU), Facultad de Ciencia y Tecnologa, Dpto. Mineraloga y Petrologa, B Sarriena s/n, 48940 Leioa (Vizcaya), Spain Dpto. Ciencias, Seccin Qumicas, Ponticia Universidad Catlica del Per (PUCP), Av. Universitaria 1801, Lima-32, Peru

a r t i c l e

i n f o

a b s t r a c t
Ln0.5M0.5FeO3 (Ln = La, Nd, Sm; M = Ba, Sr) perovskites have been synthesised by the glycine-nitrate route in order to obtain compounds with good morphological and electrical characteristics to be used as SOFC cathodes. A systematic study of the inuence of the average ionic radius of the A cation (brAN), on the structural, morphological and electrical properties of these perovskites has been performed. The obtained materials have been characterised by ICP-AES analysis, X-ray powder and neutron powder diffraction, scanning electron microscopy and four-probe conductivity measurements. In this study brAN has been changed in the range 1.34 brA N 1.25 , while keeping constant the doping level, x = 0.5 (in A position) and A cation size disorder, 2 (rA) = 0.0161 2. Overall, the sample with the higher average ionic radius showed the highest values of conductivity. Chemical compatibility of the proposed cathodes with yttria-stabilised zirconia electrolyte (YSZ) has also been analysed. The data indicate that additional phase formations exist in all systems at temperatures above ~ 1000 C. 2011 Elsevier B.V. All rights reserved.

Article history: Received 5 January 2011 Received in revised form 19 July 2011 Accepted 28 July 2011 Available online 13 September 2011 Keywords: Cathode Electrical conductivity Microstructure Perovskite structure SOFC

1. Introduction Solid oxide fuel cells (SOFCs) have been for long considered as efcient devices for the direct conversion of the chemical energy of a fuel into electrical power, combining the benets of environmentally friendly power generation with the advantage of fuel exibility [1]. Conventional SOFCs use to operate at high temperatures (800 1000 C) to maximise fuel conversion but this is also the origin of several long term problems, such as the interfacial reaction between the cathode and the electrolyte, and the degradation of the anode via particle coarsening. The use of intermediate temperatures (IT, 600 800 C) is expected to overcome some of these problems but the decrease of the performance associated with a low operation temperature is still a concern, mainly with respect to the cathode [2]. The development of new cathode materials for these temperatures is thus an active eld of research. Materials with the perovskite structure (ABO3) are the most widely studied as IT-SOFC cathodes due to the ability of this structure to tolerate extensive modications in its composition [3]. It has been demonstrated that the appropriate selection of the A- and B-site elements (or element combinations) can change their electrical and electrochemical characteristics and thus render them more useful as SOFC cathodes [4,5].

The A position is usually occupied by a mixture of rare and alkaline earths cations (Ln 3+: La, Sm, Nd, Pr and/or M2+: Sr, Ba, Ca) and the B site by a rst-row transition metal (Mn, Fe, Co) or a mixture of them [6]. Among the most studied IT-SOFC cathodes, the mixed ionic and electronic conductors La1-xSrxFeO3, La1-xSrxCoO3 or La1-xSrxCo1-yFeyO3 are worth mentioning [79]. Of these, iron based perovskites have shown low reactivity with the standard electrolyte, ytria-stabilised zirconia (YSZ), together with a good thermal expansion coefcient (TEC) matching [10,11]. Both are required characteristics for a cathode in order to avoid the side formation of unwanted and poor conducting phases in the cathode-electrolyte interphase during fabrication and operation, and also to prevent mechanical stresses that could destroy this interphase. Compounds with the general formula La1-xAxFeO3 have shown their highest electrical conductivity and the best cathode performances with intermediate x compositions (or doping levels) [1214] but are also highly dependent on other structural factors such as the tolerance factor (t) and the mean A site-radii (rA) [1518]. Moreover, it has for long been demonstrated that even the disorder of Ln3+ and M2+ cations with different sizes distributed over the A site have important implications in the properties of these type of perovskites [19]. To quantify this effect, the variance of the A-cation radius distribution, 2(rA), is used: for two or more A-site species with fractional occupancies yi (yi = 1), the variance of the ionic radii ri about the mean brAN is:

Corresponding authors at: B Sarriena s/n, 48940 Leioa, Vizcaya, Spain. Tel.: + 34 946015984; fax: + 34 946013500. E-mail addresses: ana.ecija@ehu.es (A. Ecija), maribel.arriortua@ehu.es (M.I. Arriortua). 0167-2738/$ see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.ssi.2011.07.019

rA = yi ri hrA i :

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Table 1 Series of Ln0.5M0.5FeO3 (Ln = La, Nd, Sm; M = Ba, Sr) perovskites. Ln0.5M0.5FeO3 La0.5Ba0.5FeO3 La0.34Nd0.16Sr0.12Ba0.38FeO3 La0.04Nd0.46Sr0.24Ba0.26FeO3 La0.05Sm0.45Sr0.32Ba0.18FeO3 brAN () 1.34 1.31 1.28 1.25 2(rA) (2) 0.0161 0.0161 0.0161 0.0161 t 1.02 1.00 0.99 0.98

Table 2 Summary ICP results for Ln0.5M0.5FeO3 (Ln = La, Nd, Sm; M = Ba, Sr) perovskites. Nominal composition Elemental composition La La0.5Ba0.5FeO3 La0.34Nd0.16Sr0.12Ba0.38FeO3 La0.04Nd0.46Sr0.24Ba0.26FeO3 La0.05Sm0.45Sr0.32Ba0.18FeO3 0.48(1) 0.34(1) 0.04(1) 0.05(1) Nd/Sm 0.16(1) 0.45(1) 0.44(1) Ba 0.49(1) 0.39(1) 0.24(1) 0.31(1) Sr 0.12(1) 0.26(1) 0.18(1) Fe 1.00(1) 1.00(1) 1.00(1) 1.00(1)

between 1.34 and 1.25 keeping x and 2(rA) constant, with values of 0.5 and 0.0161 2, respectively. Given that together with the structural considerations the morphological characteristics of the perovskite powders are also a key factor to be optimised for an appropriate SOFC cathode [22,23], we have also looked into an optimum synthetic method. Among the different synthetic routes, the glycine-nitrate method has been cited as a suited technique for preparing this type of perovskite cathodes as compared to traditional synthetic methods such as the ceramic route [24,25]. The main advantage of the process is that it leads to powders with large compositional homogeneity and nanometric particle sizes. Consequently, this is the method that we have chosen for the present study. 2. Experimental All Ln0.5M0.5FeO3 (Ln = La, Nd, Sm; M = Ba, Sr) perovskites (Table 1) were synthesised by the glycine-nitrate route under identical conditions. The aqueous metal-nitrate solutions were mixed with constant stirring on a hot plate. These solutions were heated to evaporate the excess of water and, afterwards, the glycine was added. A glycine/nitrate molar ratio of 2:1 was used. The mixture results in a viscous liquid which was ignited by quickly heating the solutions to approximately 400 C. The obtained powders were pelletized and calcined at 800 C for 2 h to remove carbon residues. To obtain the nal materials, these powders were again pelletized and calcined, with intermediate grindings, at 850, 950 and 1050 C. In each step, samples were kept for 10 h at the highest temperature and the process was always carried out under air.

Previous studies in similar perovskite oxides showed good cathode performances for those compounds with high average ionic radius of A-site cations and low A cation size disorder [20,21]. The aim of this work is the evaluation of the effect of the variation of brAN on the properties of four different phases proposed as possible SOFC cathodes, Ln0.5M0.5FeO3 (Ln = La, Nd, Sm; M = Ba, Sr). These properties include crystal structure, morphology and electrical conductivity. A comparative study on the reactivity of these compounds with YSZ was also performed. For this series (Table 1), brAN has been varied

Fig. 1. Rietveld ts to the X-ray powder diffraction patterns at room temperature for (a) brAN = 1.34 , (b) 1.31 , (c) 1.28 and (d) 1.25 samples.

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Compositional analyses were performed by inductively coupled plasma atomic emission spectroscopy (ICP-AES) on a Horiba Yobin Yvon Activa spectrophotometer. The structural analysis was performed using laboratory X-ray diffraction (XRD). The XRD data were collected on a Bruker D8 Advance diffractometer equipped with a Cu tube, a Ge (111) incident beam monochromator ( = 1.5406 ) and a Sol-X energy dispersive detector. Data were collected from 18 to 110, 2, (step size= 0.02 and time per step= 10 s) at room temperature (r.t.). The powder neutron diffraction (DNP) experiments were performed on the D2B instrument at the Institute Laue-Langevin: ILL (Grenoble, France), using incident neutrons of wavelength = 1.594 . Data were recorded at room temperature between 0 2 160 in steps of 0.05 on approximately 6 g of powder sample placed in a vanadium can. In both cases (neutron and X-ray patterns) the structural parameters were rened by the Rietveld method [26] using the GSAS software package [27]. The morphologies of the powder samples were observed using a scanning electron microscope (SEM, JEOL JSM-7000F). Secondary electron images were taken at 3 kV and 7 .10 12 A using a working distance of 3.8 mm. The densities of the bulk samples were determined by the Archimedes water immersion technique using sintered pellets of the samples. The electrical conductivities of the sintered samples (with approximate dimensions of 622 mm in all cases) have been measured in air by DC four-probe techniques from 900 C to r.t. Pt wires and paste were used as current collectors. The electrical conductivity values have been corrected taking into account the porosity of the samples using Eqs. (2) and (3) [28]: 0 corrected B = measured @1 + 1 Pfvol C qA 2 1 + 3 Pfvol

Given that ferrite perovskite compounds are magnetically ordered at room temperature [29,30], magnetic peaks were taken into account during renement and were indexed considering a G-type magnetic structure. In case of La0.05Sm0.45Sr0.32Ba0.18FeO3 (brAN = 1.25 ) sample, low quality data was collected due to the samarium is a strong neutron absorber element. Given that the renement of the DNP diffraction pattern did not give acceptable results the data have not included. The X-ray and neutron diffraction patterns were indexed using a cubic symmetry (S.G.: P m-3 m) for the brAN = 1.34 and 1.31 samples. The samples with lower brAN values (brAN = 1.28 and 1.25 ) were indexed with rhombohedral symmetry (S.G.: R -3c).

exp Pfvol = 1 theoretic

where exp is the experimental density calculated using the Archimedes method and theoretic is the theoretical density obtained from X-ray diffraction measurements. It is to note that the relative density (exp/theoretic) could be slightly underestimated since the formula weight used in the theoretic calculation ignores the oxygen vacancies. In order to study the chemical stability of the Ln0.5M0.5FeO3 /YSZ systems the cathode powders were mixed with a commercially-supplied yttria-stabilised zirconia (8YSZ, Tosh Corporation) in a 5050% weight ratio, using acetone to homogenise the mixtures. Thermodiffractometric (TDX) measurements on these mixtures were collected using a Bruker D8 Advance Vantec diffractometer equipped with platinum sample holder at 30 kV and 20 mA over a range of 2070 (2) (step size= 0.033; time per step = 0.4 s). The temperature was increased at a rate of 0.15 C.s 1, from r.t. to 1220 C. 3. Results and discussion 3.1. Compositional and structural study The nominal composition of the samples and the results from the ICP analysis are shown in Table 2. Within the experimental errors, the experimental compositional values for all the samples match the nominal composition. The content of the cations have been calculated considering that the stoichiometry of oxygen is 3.00 (the oxygen content values of the samples are shown below). The purity of the samples is demonstrated and details of the structure are obtained by X-ray diffraction. As well as this, to obtain information of the oxygen stoichiometry neutron diffraction measurements were performed.

Fig. 2. Rietveld ts for NPD patters at room temperature for (a) brAN = 1.34 , (b) 1.31 , and (c) 1.28 samples.

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Rietveld ts to the XRD and DNP patterns for all the compounds at room temperature are shown in Figs. 1 and 2. The lattice parameters (a, b, c), unit cell volume (V), theoretical density (), main average bond lengths (bAFeN, bAON, bFeON), FeOFe angles obtained from the renement of XRD and DNP patterns are summarised in Table 3. As well as this, information about the oxygen occupancy (Overall O occup) obtained from DNP patterns is shown. The brAN dependence of the lattice parameters and unit cell volume are shown in Fig. 3. As it can be observed, lattice parameters and unit cell volume decrease with decreasing the average A-site ionic radius and the lattice parameters as determined from neutron powder-diffraction data are consistent with the previous X-Ray diffraction determination. The oxygen stoichiometry of the samples is: 3.00(3), 2.99(1) and 2.98(1) for brAN = 1.34 , brAN = 1.31 and brAN = 1.28 , respectively, being the samples nearly stoichiometric compositions. According to the literature the volume cell of a perovskite typeABO3 is affected by the average ionic radius of the A-cation, oxygen vacancy and the formation of the mixed valence state of the B-site [31]. Given that the doping level has been xed (x = 0.5) and the samples are nearly stoichiometric compositions changes in the ratio Fe 3+/Fe 4+ are not expected. Therefore, the decrease in volume cell and lattice parameters is ascribed to the decrease in brAN. A decrease of the mean distances AO, AFe is observed with decreasing brAN. The slighter decrease observed for FeO distances is not completely unexpected given that brFeN has been kept constant. As well as this, the decrease in brAN leads to a decrease in the Fe\O\Fe bond angle, which is probably a consequence of the tilting in the FeO6 octahedra [32]. Therefore, an increase of the distortion of the perovskitetype structure is observed with decreasing mean ionic radius. The average size of the crystalline domains (coherently diffracting domains) of the samples was extracted from the broadening of the X-ray diffraction peaks using the Scherrer equation [33] (Eq. (6)): = K : B cosB 6

The calculated crystallite sizes are 90, 85, 60 and 70 nm for the samples with brAN = 1.34, 1.31, 1.28, 1.25 , respectively. 3.2. Morphological study Fig. 4 shows SEM micrographs of the powder Ln0.5M0.5FeO3 cathodes after the last heating at 1050 C. All the samples have homogeneous and porous microstructure as expected for SOFC's cathodes [34]. Although there is some particle agglomeration in all cases, image analysis of the micrographs has allowed us to determine that the average grain size of the samples is in the range of 150200 nm. These small particles are agglomerated in grains of nearly 1 m in all cases. As well as this, from the techniques used to evaluate the particle sizes (SEM and powder diffraction), it can be concluded that particles are composed of few coherently diffracting domains with roughly half the size of the particles (~70 nm vs. ~ 150 nm, respectively). 3.3. Electrical conductivity The electrical conductivity measurements of the samples after porosity correction, as in ref. [28], are illustrated in Fig. 5. In all cases the electrical conductivity increases with temperature up to a maximum and then decreases due to the lattice oxygen loss, as observed in several other cases [9,35,36]. In the present case the highest values of conductivity are observed for the sample with the highest average ionic radius. At 700 and 800 C, typical operating temperatures for the application of these materials as SOFC cathodes, the conductivity decreases with decreasing brAN. This trend is in good agreement with the one observed in the literature for similar (Ln0.5M0.5)FeO3- samples (1.25 b rA N 1.21 ; 2(rA) = 0.0030 2) [37]. However, the conductivity values for the present compounds are lower than the previously reported ones [37]. One of the possible causes of the differences between two groups of samples seems to stem from the different values of A-cation disorder. In this sense, it was clearly observed that, for a given brAN and doping level x [18] the electrical conductivity decreases as the cation size disorder increases. In the present samples, it is true that the brAN are higher than those of the samples studied in ref. [37], and higher conductivities could be expected, but it is also true that the cation size disorder is much higher in this case as well. The conductivity of the samples can be described by the smallpolaron conductivity model. In this model, the electronic conductivity is obtained via hopping of electrons from the occupied sites, Fe 3+ ions, to the unoccupied sites, Fe 4+ ions [38]. Therefore, depends on the overlap

Where is the average crystallite size in , is the wavelength of the Cu K radiation (1.54060 ), is the Bragg diffraction angle of the line, and the broadening of the peaks due to the crystallite size ( is obtained from the difference between the FWHM and the instrumental width) and K is the Scherrer shape factor (K= 0.9 was used for the calculations). The shape factor provides information about the roundness of the particle, being k = 1 for spherical particle and k b 1 for the rest of particles.

Table 3 Lattice parameters (a,c), unit cell volume (V), fractional atomic coordinates (x, y, z), oxygen occupancy (Overall O occup), magnetic moment (M) and agreement factor (2) for the series of Ln0.5M0.5FeO3 (Ln = La, Nd, Sm; M = Ba, Sr) perovskites. Compound La0.5Ba0.5FeO3 brAN = 1.34 XRD Symmetry Space group a = b () c() V/Z(3) theoretic (g/cm3) b exp (g/cm3) Overall Ooccup Magnetic moment M(B) Distance b AFe N () Distance b AO N () Distance FeO () (x6) FeOFe angle () 2
b

La0.34Nd0.16Sr0.12Ba0.38FeO3 brAN = 1.31 NDP + XRD Cubic P m-3m 3.93538(4) 60.95(1) 6.60 1.004(6) 1.6(3) 3.40814(3) 2.78274(2) 1.96769(2) 180 4.317 XRD Cubic P m-3m 3.9220(1) 60.33(1) 6.52 6.14 (6) NDP + XRD Cubic P m-3m 3.92121(3) 60.29(1) 6.52 0.998(3) 2.2(4) 3.39587(2) 2.77272(1) 1.96061(1) 180 18.29

La0.04Nd0.46Sr0.24Ba0.26FeO3 brAN = 1.28 XRD Rhombohedral R -3c 5.5181(8) 13.499(4) 59.33(4) 6.51 6.08(9) NDP + XRD Rhombohedral R -3c 5.5123(4) 13.531(1) 59.34(1) 6.50 0.994(4) 1.5(1) 3.3780(2) 2.7605(1) 1.9570(1) 170.45(8) 17.84

La0.05Sm0.45Sr0.32Ba0.18FeO3 brAN = 1.25 XRD Rhombohedral R -3c 5.5010(6) 13.457(3) 58.78(1) 6.53 6.07(3)

Cubic P m-3m 3.93652(9) 61.00(1) 6.59 6.12 (6)

3.40912(1) 2.78354(3) 1.96826(3) 180 2.063

3.39652(8) 2.77325(7) 1.96098(7) 180 1.515

3.3776(9) 2.7601(9) 1.9552(8) 170.4(8) 1.802

3.3665(3) 2.7533(4) 1.9537(5) 168.96(6) 1.999

exp is the experimental density calculated using the Archimedes method.

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between oxygen 2p-orbitals and the 3d-orbitals of the transition metal. Given that in this study the symmetry of the compounds decreases with decreasing brAN (FeOFe is reduced), the orbital overlap is smaller, which is unfavourable for the electrical conductivity [39,40]. This explains the behaviour of the electrical conductivity with brAN. The charge transfer is thermally activated and the dependence of electrical conductivity with temperature is given by the Arrhenius equation (Eq. (5)) for the small-polaron mechanism [38]:   A Ea exp T KT

where A is the pre-exponential factor, T is the absolute temperature, Ea is the activation energy and K is the Boltzmann constant. The activation energies values (Ea) are calculated from a linear t of the plots (ln (T) vs. 1000/T) in the 50500 C range. The Ea values obtained are about 0.11 eV for the 1.34 brAN 1.28 samples, being slightly lower (0.10 eV) for the sample with brAN = 1.25 , as expected. The variation observed in the Ea values with decreasing brAN is in good agreement with the similar electrical behaviour of the electrical conductivity observed for all the samples. These similar Ea values are probably due to the same doping level (concentration of electronic charge carriers) in all samples, so no signicant changes are produced in the Fe sites. 3.4. Chemical compatibility with YSZ The chemical compatibility studies between Ln0.5M0.5FeO3 (Ln = La, Nd, Sm; M = Ba, Sr) cathodes and the YSZ electrolyte has shown that some reactivity exist between both materials at high

Fig. 3. Variation of (a) lattice parameters and (b) unit cell volume with brAN for each sample.

Fig. 4. SEM micrographs of the powder samples with (a) brAN = 1.34 , (b) 1.31 , (c) 1.28 and (d) 1.25 .

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In all cases, the temperatures at which the secondary phases are formed are very similar. The (Ba,Sr)ZrO3 secondary phases appear at temperatures between 980 C and 1020 C whereas ZrO2 starts to manifest at about 1100 C. The decrease in the intensity of the diffraction peaks of the Ln0.5M0.5FeO3 phases with temperature is attributed to the transformation of these compounds into the secondary phases mentioned earlier and not to the thermal vibration of the atoms in the structure as the temperature increases.

4. Conclusions It has been observed that the change in the average ionic radius of the studied Ln0.5M0.5FeO3 perovskites (1.34 brA N 1.25 ), obtained after xing x at 0.5 and 2(rA) at 0.0161 2, has an important inuence on their structural properties. The samples with brAN = 1.34 and 1.31 have cubic (P m-3m) symmetry whereas the brAN = 1.28 and 1.25 samples present a rhombohedral (R -3c) symmetry. At room temperature, all of the samples are nearly stoichiometric compositions. The decrease in brAN also leads to a decrease in the Fe\O\Fe bond angle, which is correlated with the electrical conductivity of the samples. The electrical conductivity is higher for the samples with higher brAN and higher Fe\O\Fe bond angles (closer to the ideal 180). On the other hand, no signicant changes are observed in the morphological properties: all the compounds have a porous microstructure with grain sizes about 150 nm. The analysis of the chemical compatibility between the present cathodes (Ln0.5M0.5FeO3 samples) and the YSZ electrolyte showed that both react at temperatures higher than 950 C. The main reaction products are (Ba, Sr)ZrO3 and ZrO2. The temperature at which these compounds appear is above the operating temperature

Fig. 5. Temperature dependence of the electrical conductivity after correction for porosity (corrected) for Ln0.5M0.5FeO3 perovskites (1.34 b rAN 1.25 ).

temperatures in all cases. Fig. 6 shows the TDX measurements of Ln0.5M0.5FeO3 /YSZ mixtures from 500 C to 1220 C. As it can be observed, all the mixtures show additional phase crystallisation at temperatures greater than 950 C. The common secondary phases that appear in the diffraction patterns are BaZrO3 and/or SrBaZrO3. The appearance of these compounds depends on the content of Ba or Sr in the original phases, as observed in other works [41,42]. Together with these phases, an impurity attributed to ZrO2 is also observed for all the samples.

Fig. 6. Thermodiffractometric measurements of the 50% YSZ: 50% sample blends. brAN = (a) 1.34 , (b) 1.31 , (c) 1.28 and (d) 1.25 . All secondary phases are indicated. Pt peaks belong to the sample holder.

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for the SOFC cathode (~800 C) but is near the sintering temperatures of the cathodes. Acknowledgements This work has been nancially supported by the Consejera de Industria, Innovacin, Comercio y Turismo (SAIOTEK 2010) of Gobierno Vasco/Eusko Jaurlaritza, the Ministerio de Ciencia e Innovacin PSE12000-2009-7 (MICINN) and the Ministerio de Industria, Turismo y Comercio (CENIT 20072010). The authors thank Dr. Gabriel Cuello for his assistance with data collection at the ILL and the ILL (Grenoble, France) for the allocation of beam time. Technical and human support provided by SGIker (UPV/EHU, MICINN, GV, EJ, ESF) and Alternative Generation Systems Group of Technological Research Centre is gratefully acknowledged. A. Ecija wishes to thank UPV/EHU for funding. References
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