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Solid State Ionics xxx (2010) xxxxxx

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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

Synthesis and characterization of doped apatite-type lanthanum silicates for SOFC applications
H. Gasparyan a,b, S. Neophytides b, D. Niakolas b, V. Stathopoulos c,d, T. Kharlamova e, V. Sadykov e, O. Van der Biest f, E. Jothinathan f, E. Louradour g, J.-P. Joulin g, S. Bebelis a,
a

Department of Chemical Engineering, University of Patras, GR 26504 Patras, Greece Institute of Chemical Engineering and High Temperature Chemical Processes (FORTH/ICE-HT), GR 26504 Patras, Greece CERECO S.A.-Ceramics and Refractories Technological Development Company, GR 34100 Chalkida, Greece d Department of Applied Sciences, Technological Educational Institute of Chalkida, GR 34400 Psahna, Greece e Boreskov Institute of Catalysis SB RAS, 630090 Novosibirsk, Russia f Department of Metallurgy and Materials Engineering, Katholieke Universiteit Leuven, B-3001 Heverlee, Belgium g CTI Cramiques Techniques et Industrielles SA, F-30340 Salindres, France
b c

a r t i c l e

i n f o

a b s t r a c t
A series of iron- and/or aluminium-doped apatite-type lanthanum silicates (ATLS) La9.83Si6 x yAlxFeyO26 (x= 0, 0.25, 0.75, and 1.5, y = 0, 0.25, 0.75, and 1.5) were synthesized using the mechanochemical activation (MA), solid state reaction (SSR), Pechini (Pe) and solgel (SG) methods. The total conductivity of the prepared materials was measured under air in the temperature range 600850 C using 4-probe AC impedance spectroscopy. Its dependence on composition, synthesis method, sintering conditions and powder particle size was investigated. It was found that for electrolytes of the same composition, those prepared via mechanochemical activation exhibited the highest total specic conductivity, which was improved with increasing Al- and decreasing Fe-content. The highest conductivity value at 700 C, equal to 2.04 10 2 S cm 1, was observed for the La9.83Si5Al0.75Fe0.25O26 electrolyte. La9.83Si4.5Fe1.5O26 electrolyte samples synthesized using the Pechini method exhibited higher conductivity when sintered conventionally than when spark-plasma sintering (SPS) was used. 2010 Elsevier B.V. All rights reserved.

Article history: Received 1 September 2009 Received in revised form 25 August 2010 Accepted 22 November 2010 Available online xxxx Keywords: Apatites Lanthanum silicates Oxide ion conductors Solid oxide fuel cells SOFC

1. Introduction Solid oxide fuel cells (SOFCs) have experienced phenomenal progress in the last two decades because of their high efciency, fuel exibility and low pollutant emissions. Yttria stabilized zirconia ZrO2 (Y2O3) or YSZ, an O2 conductor, is used as solid electrolyte in the state-of-the-art SOFCs. However, YSZ is relatively expensive and performs efciently at high temperatures (8001000 C), at which degradation of SOFC components is fast, resulting in reduction of the SOFC useful life. Development of low cost solid electrolytes exhibiting high ionic conductivity at reduced temperatures is one of the key issues for development and commercialization of intermediate temperature (600850 C) solid oxide fuel cells (IT-SOFCs). Apatite-type (general formula 10 xM6O26 , where A = rare earth or alkaline earth, M = Si, Ge, P, V, Zn) lanthanum silicates (ATLS) [19] exhibit high oxide ion conductivity at intermediate temperatures (e.g. ~ 0.03 S cm 1 at 700 C, for La10Si5.5Al0.5O26.75 [7,8]) and thus have attracted signicant attention as promising electrolytes,

alternative to YSZ, for IT-SOFCs [9,10]. The ionic conduction in apatites is dominated by the interstitial migration mechanism [8,11,12]. The apatite structure is tolerant to extensive aliovalent doping, which has been applied in the case of lanthanum silicates for improving oxide ionic conductivity [614]. In this work are presented results concerning the effect of composition (doping), method of synthesis and sintering procedure on the conductivity of iron- and aluminium-doped ATLS La9.83Si6 x yAlxFeyO26 (x= 0, 0.25, 0.75, and 1.5, y = 0, 0.25, 0.75, and 1.5). 2. Experimental 2.1. Preparation of samples detailed list of the tested apatitic electrolytes, including their nominal compositions and preparation data, is presented in Table 1. The powders of the apatite samples were prepared via the mechanochemical activation (MA) [2,15], solgel (SG) [3], solid state reaction (SSR) [6,16] and Pechini (PE) or modied solgel [1719] methods. To synthesize doped ATLS via mechanochemical activation amorphous SiO2 (REACHIM, 99.9%), La2O3 (VEKTON, 99.99%), Al(OH)3 (REACHIM, 99.5%) and Fe2O3 (REACHIM, 99.5%) were used. SiO2 and La2O3 were not

Corresponding author. E-mail address: simeon@chemeng.upatras.gr (S. Bebelis). 0167-2738/$ see front matter 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.ssi.2010.11.025

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Table 1 Composition, powder preparation method and particle size, total conductivity at 700 C and activation energy for conduction corresponding to the tested ATLS samples. Composition Particle size D0.5/m 43.5 47.6 20.7 5.6 14.0 9.8 47.0 4.0 20.9 9.8 4.0 4.0 4.0 0.8 2.5 20.1 Sintering temperature Tsint/C 1600 (4 h) 1600 (4 h) 1600 (4 h) 1500 (1 h) 1550 (1 h) 1500 (1 h) 1500 (1 h) 1500 (1 h) 1500 (1 h) 1450 (1 h) 1450 (1 h) 1450 (4 h) 1450 (10 h) 1200 (2 min) 1550 (5 h) 1500 (4 h) Conductivity at 700 C /S cm 1 204 10 4 151 10 4 116 10 4 1.07 10 4 1.29 10 4 0.41 10 4 0.45 10 4 1.18 10 4 0.79 10 4 0.87 10 4 0.55 10 4 1.45 10 4 1.01 10 4 12.2 10 4 23.5 10 4 1.96 10 4 Activation energy for conduction Ea/eV 0.57 0.61 0.66 0.99 0.96 1.03 0.94 0.71 0.73 1.00 0.98 0.70 0.75 1.12 0.93 0.75

La9.83Si5Al0.75Fe0.25O26 La9.83Si5Al0.25Fe0.75O26 La9.83Si4.5Fe1.5O26 La9.83Si5Al0.25Fe0.75O26 La9.83Si4.5Fe1.5O26 La9.83Si4.5Fe1.5O26 (ne) La9.83Si4.5Fe1.5O26 (coarse) La9.83Si4.5Al1.5O26 (ne) La9.83Si4.5Al1.5O26 (coarse) La9.83Si4.5Fe1.5O26 (ne) La9.83Si4.5Al1.5O26 (ne) La9.83Si4.5Al1.5O26 (ne) La9.83Si4.5Al1.5O26 (ne) La9.83Si4.5Fe1.5O26 ** (SPS) La9.83Si4.5Fe1.5O26 ** La9.83Si4.5Al1.5O26 *

Mechanochemical activation (MA), Solid state reaction (SSR), *Solgel method (SG), and **Pechini method (PE). D0.5: 50 % of particles under this size, SPS: Spark-plasma sintering.

calcined prior to mechanochemical activation, while all parent compounds were characterized by X-ray diffractometry (XRD), infrared (IR) spectroscopy and thermal analysis in order to obtain the stoichiometry of the target sample. Then mixtures of the parent compounds were activated for 35 min in a high-power (1200 rpm) planetary ball mill AGO-2 (steel drums and balls, sample-to-ball mass ratio 1/20) and then calcined at 1200 C for 6 h. In the case of the solgel method, stoichiometric amounts of La(NO3)36H2O (Alfa Aesar, 99.9%), Al(NO3)39H2O (Merck, for analysis, 98.5%) and TEOS (Aldrich, puriss grade, 99.0%) were dissolved in absolute ethanol (Merck, for analysis, min. 99.8% ), glacial acetic acid (Merck, for analysis, min. 99.8%) and double distilled water. The resulted sol was aged overnight (TN 60 C). After drying, the precursor was calcined at 1000 C in air. In the case of the Pechini (modied solgel) method the procedure was similar to the aforementioned solgel route, the difference being that ethylene glycol and citric acid were used as gelling agents, as described in detail elsewhere [18,19]. The gel was calcined at 900 C in air and then ball milled for 48 h [18,19]. In the solid state reaction method appropriate amounts of the relevant oxides, namely SiO2 (Rhodia, 99%), La2O3 (Rhodia, 99.9%), Fe2O3 (Minraux Industrielles de Gaillon, 98.5%) and Al2O3 (Rio Tinto Alcan, 99.8%) were homogenized by ball milling, red at 1400 C and then crushed, milled, homogenized and red once again at 1400 C. After this ring, they were crushed again and nally milled into powder. La2O3 was calcined in air at 700 C for 2 h prior to mixing with the other oxides. The powder received in this way is denoted as coarse in Table 1. Part of the coarse powder was further milled to form the ne powder (Table 1). The powder of each material prepared via the MA, SG and SSR methods was pressed into pellets (disks) and sintered in air at temperatures 1200 to 1600 C (heating and cooling rates of 10 C min 1) to form dense structures (approximately 9598% relative density), as shown using scanning electron microscopy (SEM) and porosity measurements. In the case of the powders prepared via the Pechini method, spark-plasma sintering (SPS) [19] in vacuum at 1200 C (60 MPa pressure, 2 min dwell time, 100 C min 1 heating rate) in addition to conventional (pressureless) sintering (1550 C for 5 h, heating and cooling rates of 20 C min 1) was applied, resulting in structures of approximately 97 and 94% relative density, respectively. The aim of additionally using SPS was to obtain samples having relative density higher than 95% after sintering at lower temperatures compared to conventional sintering as well as to obtain ne grain size (nanometer size) in order to study the inuence of the grain size on conductivity via comparison with the conventionally sintered samples which had coarser grain size, as shown below. The grain size of the sintered samples was checked using SEM while the particle size of the

corresponding powders was determined using a Mastersizer particle analyzer (Malvern Instruments, UK). In all cases the formation of apatite structure was evidenced by XRD. The presented XRD data were collected (Siemens D 500 X-ray diffractometer) at room temperature over the 2 range of 1580 at a rate equal to 0.02 s 1, using monochromated Cu-K radiation. 2.2. Experimental set-up Total specic conductivity measurements of apatite pellets (disks) were carried out in a single chamber cell of approximately 30 cm3 volume, described in detail elsewhere [20]. The impedance spectra were obtained in air at temperatures 600 to 850 C, using a symmetric set-up of two platinum electrodes deposited on the two sides of the electrolyte. The Pt porous electrodes were deposited by applying thin coatings of a Pt organometallic paste (Engelhardt M603B) on the apatite disks, followed by calcining rst in 400 C for 60 min and then in 830 C for 30 min. The samples were clamped inside the single chamber cell using two Au plates pressed on both sides of the disk between two non-conductive ceramic slabs. These Au plates covered the Pt electrodes almost entirely and were connected via 4-Au wires (two for each plate) with the external electric circuit. The AC impedance measurements were carried out using a Princeton Applied Research 263A potentiostatgalvanostat combined with a Princeton Applied Research 5210 dual phase lock-in amplier. The applied stimulus amplitude in the AC impedance measurements was 10 mV and the widest frequency range was 10 mHz100 kHz. The ohmic resistance of each sample, on which the specic conductivity calculation was based, was determined from the intersection of the corresponding Nyquist plot with the Zreal (real part of the impedance) axis at high frequencies, referring to that part of the plot which did not change upon polarization. The magnitude of the capacitances corresponding to the individual arcs in the Nyquist plots was taken into account in order to assign them to contributions of the different processes [3,16]. 3. Results and discussion In Fig. 1a and b are shown scanning electron microscopy (SEM) pictures of the top view (Fig. 1a.1 and b.1) and cross section (Fig.1a.2 and b.2) of the La9.83Si4.5Fe1.5O26 electrolyte samples prepared via mechanochemical activation (MA) and solid state reaction (SSR), respectively, while in Fig. 1c are shown SEM pictures of the top view of the La9.83Si4.5Fe1.5O26 samples prepared via the Pechini method

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Fig. 1. SEM images of selected ATLS samples (Table 1): (a) La9.83Si4.5Fe1.5O26 (MA) (a.1: top view, a.2: cross section), (b) La9.83Si4.5Fe1.5O26 (SSR, Tsint: 1550 C ) (b.1: top view, b.2: cross section) and (c) La9.83Si4.5Fe1.5O26 (PE) (c.1: conventional sintering, c.2: SPS).

followed by pressureless (Fig. 1c.1) or spark-plasma sintering (Fig. 1c.2), respectively (Table 1). The SEM pictures (Fig. 1) show the existence of signicant differences in the microstructure of the dense pellets depending on composition, synthesis method and sintering conditions. In Fig. 1b, for the sample prepared by SSR is observed great variation regarding grain size as well as sinterability. This may be due to local variations in composition causing the formation of phases with differences in sintering behavior. As solgel or MA methods achieve material precursors of high chemical homogeneity, no such side reactions are expected and a much more uniform grain microstructure is observed (Fig. 1a and c). The

conventionally and spark-plasma sintered (SPS) samples (Fig. 1c) exhibit uniform microstructure but with signicantly different grain size. However such small grain microstructure is expected for the SPS sample (Fig. 1c.2) in comparison with the conventionally sintered sample (Fig. 1c.1) due to the rapid sintering step. In Fig. 2 are presented typical normalized XRD patterns of the La9.83Si4.5Fe1.5O26 electrolyte sample prepared via solid state reaction and sintered at 1550 C for 1 h, of the La9.83Si4.5Fe1.5O26 , La9.83Si5Al0.75Fe0.25O26 and La9.83Si5Al0.25Fe0.75O26 samples prepared via mechanochemical activation and sintered at 1600 C for 4 h as well of the La9.83Si4.5Al1.5O26 sample prepared via the solgel

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200 a.u.
(a) (b)
La9.83Si4.5Fe1.5O26 1600 C (4h - MA)
o

La9.83Si4.5Al1.5O26 1500 C (4h - SG)

Intensity (a.u)

(c)
La9.83Si5Al0.75Fe0.25O26 1600 C (4h - MA)
o

(d)
La9.83Si5Al0.25Fe0.75O26 1600 C (4h - MA)
o

(e)
La9.83Si4.5Fe1.5O26 1550 C (1h - SSR)
o

10

20

30

40

50

60

70

80

2, deg
Fig. 2. Typical XRD patterns of electrolytes prepared via solid state reaction (SSR) and sintered at 1550 C for 1 h, via mechanochemical activation (MA) and sintered at 1600 C for 4 h, as well as via the solgel method (SG) and sintered at 1500 C for 4 h (Table 1).

method and sintered at 1500 C for 4 h (Table 1). These XRD patterns match the JCPDF le card 49-0443 corresponding to the standard pattern for undoped lanthanum silicate (La9.33Si6O26) and thus reveal that the samples presented in Fig. 2 were mainly comprised of the apatite-phase. This was also the case for all tested materials prepared via the aforementioned methods as well as those prepared via the Pechini method [18,19]. It is noted, that the higher background observed at low 2 in the case of the La9.83Si4.5Fe1.5O26 prepared via is due to the fact that part of the sample holder was exposed to the X-ray beam as its diameter was smaller than that of the specic sample. Fig. 3a shows in the form of an Arrhenius plot, in the temperature range 600850 C, a comparison of the calculated total specic conductivities in air of the best performing ATLS samples prepared using different methods (Table 1) as described above. In Fig. 3b and c are presented complex impedance plots (Nyquist plots) obtained at 600 C in air with a selection of the aforementioned samples (Fig. 3b) and Nyquist plots obtained in air at different temperatures with sample La9.83Si5Al0.75Fe0.25O26 prepared via MA (Fig. 3c), which exhibited the highest total specic conductivity among all samples. As shown in Fig. 3a, for electrolytes of the same composition, powders prepared via mechanochemical activation resulted in pellets exhibiting specic conductivity higher than that of pellets prepared using the other methods. The conductivity of the apatite electrolytes prepared via MA seems to be improved with increasing Al- and decreasing Fecontent (Fig. 3a), the highest conductivity obtained with sample La9.83Si5Al0.75Fe0.25O26 . The same conclusions result from comparison of the total conductivity at 700 C, the value of which for all tested samples is listed in Table 1 along with the corresponding activation energy for conduction Ea. Increase in total conductivity with increasing Al- and decreasing Fe-content was also observed for apatite electrolytes prepared from powders of similar particle size (4 to 9.8 m) synthesized via SSR and sintered at 1500 C for 1 h. This is shown in Table 1 for 700 C and was also the case for lower temperatures. However, the opposite trend was observed by comparing samples sintered at 1450 C for 1 h (Table 1), which does

Fig. 3. (a) Temperature dependence of the total specic conductivity in air of the best performing ATLS samples prepared via different methods (Table 1). The dotted line corresponds to YSZ [21] and is shown here for comparison. (b) Complex impedance plots (Nyquist plots) obtained at 600 C in air with a selection of the aforementioned samples (the same symbols as in (a) are used). (c) Nyquist plots obtained in air at different temperatures with sample La9.83Si5Al0.75Fe0.25O26 prepared via MA (the best performing among all samples).

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sintered pellets, are needed in order to reach a solid conclusion concerning the effect of particle size on the conductivity of the dense electrolyte samples. 4. Conclusions Comparison of the total conductivities of ATLS electrolyte samples prepared using powders synthesized via mechanochemical activation (MA), solid state reaction (SSR), solgel (SG) or Pechini (modied solgel) route showed that mechanochemical activation results in electrolyte samples exhibiting the best performance concerning conductivity, their conductivity characteristics being improved by increasing Al- and decreasing Fe-content. Concerning the electrolyte samples prepared using SSR, for those doped solely with Al the optimal sintering conditions corresponded to 1450 C for 4 h, while for those doped solely with Fe they corresponded to 1550 C for 1 h. Furthermore, for the electrolytes doped solely with Al it was found that a smaller particle size of the powder resulted in an increase of the total conductivity. In the case of Fe-doped electrolytes prepared using the Pechini method, conventional (pressureless) sintering resulted in samples with higher conductivity compared to that of samples of the same composition prepared using spark-plasma sintering (SPS). Acknowledgement not allow for drawing general conclusions and implies the need for further systematic study. Comparison of the conductivities of the La9.83Si4.5Fe1.5O26 electrolytes prepared via the Pechini (modied solgel) method shows that pressureless sintering resulted in a sample with conductivity higher than that of the sample sintered using the SPS technique (Fig. 3a). The conductivity of the former sample at 700 C was close to that of sample of the same composition prepared by Shaula et al. [6] via a SSR route. Compared with samples of the same composition prepared via SSR, the conductivity of sample La9.83Si4.5Al1.5O26 prepared via the solgel route was higher than that of samples prepared in the present work (Table 1) but signicantly lower than that of samples prepared by Shaula et al. [6]. Comparison of the conductivities of samples prepared from solely Fe-doped or Al-doped electrolyte powders of the same or similar particle size synthesized via SSR and sintered for the same time (1 h) at different temperatures or at the same temperature (1450 C) for different times, respectively, reveals the existence of a set of optimal sintering conditions in each case. For the SSR prepared samples doped solely with Al the optimal sintering conditions corresponded to 1450 C for 4 h, while for those doped solely with Fe they corresponded to 1550 C for 1 h. The effect of electrolyte powder particle size on conductivity is shown in Fig. 4, where the total conductivities of La9.83Si4.5Al1.5O26 samples prepared using the SSR method and the same sintering conditions (1500 C for 1 h) but corresponding to different powder particle size (4 m or 20.9 m, Table 1) are compared at different temperatures. The inset in Fig. 4 shows the corresponding Nyquist plots obtained at 600 C. The comparison shows that the La9.83Si4.5Al1.5O26 sample prepared starting from ne powder performed better than that prepared starting from coarse powder. Obviously, additional experiments with electrolyte powders of varying composition and well dened particle sizes, in combination with determination of the grain sizes in the Financial support by the European program STREP: MATSILC 033410 Novel Materials for Silicate-Based Fuel Cells is gratefully acknowledged. References
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Fig. 4. Temperature dependence of the total specic conductivity of La9.83Si4.5Al1.5O26 samples prepared via solid state reaction from powders of different particle size (ne: 4 m, coarse: 20.9 m, Table 1). Inset: Corresponding Nyquist plots obtained in air at 600 C.

Please cite this article as: H. Gasparyan, et al., Solid State Ion. (2010), doi:10.1016/j.ssi.2010.11.025