Ceramics International xxx (xxxx) xxx

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Effect of sintering temperature on the transport properties of La2Ce2O7

ceramic materials
Bishnu Choudhary a, b, Sharmistha Anwar a, Dmitry A Medvedev c, Laxmidhar Besra a,
Shahid Anwar a, *
a
CSIR-Institute of Minerals and Materials Technology, Bhubaneswar, Odisha, India
b
AcSIR- Academy of Scientific and Innovative Research, Ghaziabad, Uttar Pradesh, India
c
Hydrogen Energy Laboratory, Ural Federal University, Ekaterinburg, Russia

A R T I C L E I N F O A B S T R A C T

Keywords: La2Ce2O7 (LCO) based materials are of a paramount importance since they can be utilized for ammonium pro­
La2Ce2O7 duction, thermal barrier application, catalysts, hydrogen production and solid oxide fuel cells (SOFCs). In this
Sinterability work, a nano crystalline LCO powder was prepared using glycine-nitrate combustion method and then its
Impedance spectroscopy
properties were comprehensively characterized. The structural analysis of the synthesized LCO was carried out
Distribution function of Relaxation times
using conventional X-ray diffraction (XRD) and Raman spectroscopy. In a disordered phase, LCO is a biphasic
mixture composed of C- and F-type phases. Densification studies were performed by sintering LCO pellets at
different sintering temperatures. A densification of ≥95% was observed in all the samples with a very little
variation. Sintering temperature had a marked effect on the electrical conductivity of LCO. The LCO sintered at
1100 ◦ C showed the highest conductivity (3.68 mS/cm at 700 ◦ C in air). The electrical conductivity was found to
be decreasing with an increase in sintering temperature from 1100 to 1400 ◦ C. To understand the behavior, the
analysis of distribution function of relaxation times (DFRTs) utilized for correct separation of grain and grain
boundary resistances. The presence of C- and F- type phases calculated from Raman spectra plays a crucial role in
deciding conduction behavior of LCO. The results suggest a strong relationship between history of the ceramics
preparation and their electrical properties.

1. Introduction electrolytes. High temperature requirement is the limitation for

commercialization. High temperature operation demands specific and
Solid oxide fuel cell (SOFC) is an electrochemical device which expensive interconnects and the thermal stresses generated in SOFCs. Y
provides electrical energy by a series of electrochemical reactions. and Ce doped barium zirconates are gaining popularity because of their
SOFCs offer many advantages over other fuel cell types such as fuel proton conductivity its low temperature (400–700 ◦ C) [1,2,5]. Apart
flexibility, reliability with very low levels of pollutant emissions, no from the conducting nature of these electrolyte materials, their sintering
involvement of corrosive liquid to the cells [1,2]. Essentially, SOFCs ability is also one of the important factor for its quality control. The
consist of two porous electrodes separated by a dense electrolyte which electrolyte, which is sandwich between electrodes, should be highly
generate electricity by the flow of electrons from the fuel electrode dense to avoid any mixing of reactant gases (such as hydrogen and ox­
(anode) to air electrode (cathode). The current is obtained via transfer of ygen) during SOFC operation.
oxide ions/protons throughout the electrolyte, which is thermally active Generally, oxide-ion conducting electrolytes such as YSZ, doped
process [1,3,4]. In the last two-decades, a numerous researches have ceria, LSGM, scandium stabilize zirconia (ScSZ) are reported to be high
been carried out for development of electrolyte materials for SOFCs. sintering temperature materials above 1300◦ C [6–10] without any help
There are various well studied electrolyte materials, such as yttria sta­ of sintering aids. However, some researchers have attempted to reduce
bilize zirconia (YSZ), doped ceria, La0.9Sr0.1Ga0.8Mg0.2O3− δ (LSGM), and the sintering temperature using sintering aids such as ZnO, CuO etc.
doped barium zirconates. Among them, YSZ, doped ceria, and LSGM are however, the sintering aid elements have been reported to show detri­
normally categorized into high temperature oxygen-conducting mental effect of grain boundary conductivity [11–13]. Doped barium

* Corresponding author.
E-mail addresses: [email protected], [email protected] (S. Anwar).

https://doi.org/10.1016/j.ceramint.2021.11.227
Received 4 September 2021; Received in revised form 9 November 2021; Accepted 23 November 2021
Available online 26 November 2021
0272-8842/© 2021 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Please cite this article as: Bishnu Choudhary, Ceramics International, https://doi.org/10.1016/j.ceramint.2021.11.227
B. Choudhary et al. Ceramics International xxx (xxxx) xxx

zirconates based electrolyte materials as proton conducting oxides present in it.

exhibit sufficient protonic conductivity but due to its refractory nature it Phase purity of synthesized powder were characterized by the X-ray
requires high temperature sintering (>1500 ◦ C) that makes diffraction (XRD) technique (Rigaku Ultima IV) using Cu Kɑ radiation
manufacturing processes uneconomical. In addition, high temperature with λ = 0.15406 nm over a 2θ range of 20–80◦ . The synthesized powder
sintering can introduce non-stoichiometry in doped barium zirconate was pressed in a 10 mm pellet using a hydraulic press and sintered at
system due to evaporation of barium at high temperature [14,15]. Low various temperatures (1000, 1100, 1200, 1300 and 1400 ◦ C) for 5 h. The
temperature sinterability of electrolyte materials can be advantageous in particle morphology, surface morphology of sintered samples and their
terms of ease of materials processing, economy and time reduction. average grain size (of ~ 100 grains) was examined by using TEM (FEI,
Moreover, the low temperature sintering of electrolytes, especially for Tecnai G2 20 Twin, Netherland), Field Emission Scanning Electron Mi­
planner type cells, avoids the coarsening of nickel oxides in the anode croscope (Carl Zeiss, SUPRA GEMINI55) and Image J software
layer of SOFCs. The coarse Ni metal may affect the mechanical strength respectively.
and performance of the anode supported SOFCs [16–18]. The impedance spectra were recorded using an alternating-current
Pyrochlore based compounds having typical formula A2B2O7, Impedance analyzer (IM3570 Impedance analyzer, Hioki, Japan) and
particularly La2Ce2O7 (LCO), possess high thermal stability [19–21] and the frequency range was kept from 4 Hz to 5 MHz in air medium in a
due to the existence of an 8a lattice oxygen vacancy, most of the pyro­ temperature range of 300–700 ◦ C in an interval of 50 ◦ C with a signal
chlore compounds have good oxygen ionic conductivity [22]. LCO based amplitude of 50 mV. For better current collectivity from the sintered
compounds exhibit multifunctional properties such as catalysis [23], pellets, a silver paste was coated on either side of the sintered electrolyte
ammonium synthesis [24], thermal barrier coatings [20], solid oxide pellets and heated at 800 ◦ C for 2 h to evaporate the organics available in
fuel cells [22,25–27] etc. In SOFCs, LCO is gaining popularity because of silver paste. The total conductivity of LCO ceramics were calculated by
its chemical stability and comparative ionic/protonic conductivity over fitting the impedance spectra with various circuit elements with the help
barium zirconate based electrolytes [25,27]. In literature, it is reported of Zsimpwin software. For accurate analysis, the contribution of grain
that LCO also exhibit intrinsic sintering resistance property and it and grain boundary resistances in the LCO system was evaluated using
contain open porous structure ever after sintering at 1500 ◦ C [28]. In Distribution Function of Relaxation Time (DFRT) analysis of impedance
most of the SOFCs fabrication studies, the electrolyte materials are spectroscopy data with the help of ISGP software from Impedance
usually sintered at a very high temperature (~1400–1500 ◦ C) to densify spectra.
its microstructure [7,8,25–27,29]. However, studies on the effect of
sintering temperature on grain size and corresponding electrical con­ 3. Results and discussions
ductivity of LCO ceramics is still lacking. Engineering the grain and
grain boundary architectures in polycrystalline ceramic electrolytes can 3.1. Structural characterizations
be an effective way to improve their electrical properties. Therefore,
establishment of optimum control of grain and grain boundary con­ Fig. 1 displays the XRD pattern of the calcined La2Ce2O7 powder. The
ductivities in polycrystalline LCO ceramic is needed. most intense peak was observed at an angle (2θ) 27.67◦ which corre­
There is no consensus regarding the crystal structure of LCO and the sponds to the (111) crystallographic plane. Others prominent peaks
many contradictory results are reported in the literature. Some of the were also visible in spectrum at 32.07◦ , 46.01◦ , 54.54◦ , 57.16◦ , 67.11◦ ,
researches have suggested that it exists as a pyrochlore structure, 74.08◦ , 76.36◦ and 85.27◦ which correspond to (200), (220), (311),
whereas a few other reports suggests it as a disordered fluorite phase; in (222), (400), (331), (420) and (422) planes, respectively. The obtained
addition, a mixture of C-type and fluorite type phases was also reported diffraction peaks match well with the JCPDS 04-012-6396 data showing
[22,27,30]. Therefore, understanding LCO structure is also an important no impurities. This indicates that the reaction between precursors was
step to quantify its properties. completed during calcination at 800 ◦ C itself and it got turn into a pure
In this work, nano-sized LCO powder synthesized using a glycine- phase of LCO. The calculated lattice parameter was found to be 5.575 Å.
nitrate combustion method is extensively studied the effect of sinter­ XRD peak positions and intensity are in line with a disordered cubic
ing temperature on electrical properties of LCO ceramics. The role of (Fd3-m space group) fluorite phase of LCO, which is in agreement with
sintering temperature in defining the microstructure (grain and grain the previous reports [30,31]. However, whether its structure is fluorite
boundary) was presented. The contribution of grain and grain boundary or C-type is still not clear [30]. It is very difficult to distinguish between
in ionic conductivity is studied using DFRT (using Impedance spec­
troscopy genetic programing software with MATLAB) analysis of the
obtained impedance data.

2. Experimental

Synthesis of La2Ce2O7 (LCO) powder was performed using a glycine

nitrate combustion route. The precursor materials used were La
(NO3)2⋅6H2O (Finar, 99.9%), Ce(NO3)2⋅6H2O (Finar, 99.95%), and
glycine (99%). Stoichiometric amounts of metal nitrates were dissolved
together in 50 ml of distilled water to get metal nitrate solution. An
aqueous solution of fuel, i.e. glycine, was mixed with the metal salts
solution. The molar ratio of oxidant to fuel was kept to approx. 1:6.5.
The solution was then stirred for 10 min for homogenizing and mixing
then heated at about 250 ◦ C with continuous mechanical stirring to
evaporate excess water, resulting in formation of a sticky transparent
viscous gel. In order to carry out the gel decomposition, the viscous
solution was allowed to remain at 300 ◦ C for some more time which
resulted in self-ignition. The spontaneous combustion lasted for about
15–20 s and finally gave rise to a light yellowish powdered product. The
resultant powder was mixed thoroughly and calcined at 800 ◦ C for 6 h in Fig. 1. XRD spectra of LCO powder calcined at 800 ◦ C and its comparison with
open air to complete the reactions and eliminate impurities, if any JCPDS data.

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B. Choudhary et al. Ceramics International xxx (xxxx) xxx

a mixture of fluorite and C-type phases in LCO by conventional in Fig. 2(a)) which was responsible for oxidative coupling of methane
diffraction techniques because of large degree of similarity in both the (OCM) catalysis [23]. Peak Intensity related to surface oxygen vacancy
structures [30]. For a pyrochlore compound, which has a general mo­ was found to be increasing with sintering temperature suppressing the
lecular formula A2B2O7, the rA3+/rB4+ ratio (RAB) determines the phase intensity of F2g band (in Fig. 2(a)) at 1400 ◦ C. The symmetrical
structure stability of compounds. If the radius ratio (RAB) falls between stretching vibration mode of O–Ce in a six-fold coordination at around
1.46 and 1.76, phase structure will be considered as an ordered cubic 350 cm-1 is assigned to C-type phase structure. It clearly indicates that
pyrochlore, whereas if the radius ratio is above 1.78 or below 1.46, a the intensity of 350 cm-1 band become more and more intense when
phases of monoclinic layered perovskite or disordered defective fluorite sintering temperature increases. C/F intensity ratio (I350/I453) was also
will be formed, respectively [32]. For LCO, the calculated radius ratio is found to be increasing from 0.65 to 0.80 in samples sintered from 1000
1.33 which is lower than a threshold value of 1.46, suggesting the for­ to 1400 ◦ C (shown in Fig. 2(b)) respectively. In addition, band at 266
mation of disorder defective cubic fluorite phase instead of ordered cm-1 can also be recognized as the formation of oxygen vacancies
pyrochlore phase [32,33]. The structure can also be verified by toler­ (represented as O2 in Fig. 2(a)) [30]. Superoxide O2− and peroxide O22−
ance (τ) factor calculation based on pyrochlore compounds. The toler­ are also detected on Raman spectra at 987 and 805 cm-1, respectively
ance factor was calculated according to equation (1) which is well [23]. The Raman spectra is clearly eliciting that LCO is a biphasic
established for pyrochlore phase in literature [34]. mixture of C-type and fluorite phases, similar to those observed in other
literature [30]. Raman spectra peak positions and the corresponding
3(RA + RO )
τ = √̅̅̅̅̅ (1) band of LCO is presented in Table1. Therefore, Raman interpretation of
17(RB + RO ) LCO indicates that there is a partial interconversion of F phase to C-type
Using above equation, Zhen et al. [18] has recently reported the phase and the amount C- type phase structure increases with increase in
tolerance factor of more than 180 numbers of A2B2O7 based compounds sintering temperature.
and categorized them into four different types of pyrochlore phases: (a)
normal pyrochlore, (b) high-disorder, (c) reverse-disorder, and (d) non 3.2. Morphological and sintering behavior of LCO
pyrochlore. Based on this analysis, the tolerance factor value of normal
pyrochlore are scattered in a range of 0.83–0.94. The tolerance factor of The morphological appearances of calcined (800 ◦ C for 6 h) LCO
compounds below threshold range (i.e., <0.826) are high disorder power were determined through FESEM and TEM techniques. The
pyrochlores and above threshold range (>0.943) are non pyrochlore observed micrographs are presented in Fig. 3. FESEM and TEM images
compounds whereas τ below 0.73 is for reverse disorder pyrochlore show that there is a growth of very fine homogeneously distributed
phases. In our case, the theoretically calculated τ for LCO was found to particle in nano dimension. There is very less variation of particle size
be 0.82, on comparing with tolerance factor database, it illustrates that throughout the investigated area. The average particle size calculated
LCO belongs to high disorder phases. Therefore, both theoretically through TEM micrograph is less or close to 20 nm.
calculated radius ratio and tolerance factor confirms that LCO is proven In order to evaluate the compaction properties (dense structure) of
to be disordered fluorite phase. However, there is no sign of C-type LCO material, pellet was sintered at different temperatures. The surface
phase from the above studies. effect and sintering behavior were evaluated using FESEM images as
In order to distinguish the presence of fluorite or C- type phase in the shown in Fig. 4(a–e). Density of all the sintered samples was found to be
present compound, LCO was further characterized by the Raman spec­ almost same across all the sintering temperature from 1000 to 1400 ◦ C.
troscopy analysis. The normalized Raman spectrum of LCO ceramic This is clearly verified by the calculated density of LCO (≥95–98%) by
sintered in the temperature range of 1000–1400 ◦ C is illustrated in
Fig. 2. Normally, A2B2O7 based pyrochlore compounds have a maximum Table 1
of six Raman band of A1g + Eg+4F2g modes e.g., Y2Sn2− xZrxO7 [35]. But Raman spectra peak positions of LCO.
in most of the cases few bands are absent due to some disordering in LCO Wavelength (cm-1) Corresponding representation References
structure. In our case also, few bands are absent in LCO synthesized by
266 Oxygen vacancy [30]
glycine nitrate combustion in consistent with others reported in the
350 C-type phase [30]
literature for LCO [23]. As shown in Fig. 2 (a), two strong peaks were 453 F2g [23,25,30]
observed at 453 and 579 cm-1 which are associated with F2g band and 579 Oxygen vacancy [23,30]
oxygen vacancy respectively. The oxygen vacancy band at around 579 805 O2-2 [23]
987 O2- [23]
cm-1 has been also referred as surface oxygen vacancy (designated as O1

Fig. 2. (a)Normalized Raman spectra of LCO pellets sintered at different temperature calcined at 800 ◦ C. (b) intensity ratio against sintering temperature.

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B. Choudhary et al. Ceramics International xxx (xxxx) xxx

Fig. 3. (a) FESEM images of calcined LCO powder (b) Enlarged view of FESEM image and (c) TEM images of LCO.

Fig. 4. FESEM images of LCO pellets sintered at various temperature (a) 1000 ◦ C, (b) 1100 ◦ C, (c)1200 ◦ C, (d)1300 ◦ C and (e)1400 ◦ C.

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Table 2 temperature sinterability behavior even at low temperature of 1000 ◦ C.

Properties of LCO sintered at various temperature: relative density, gain size,
total conductivity in air at 700 ◦ C and activation energy.
3.3. Impedance spectroscopy and distribution function of relaxation times
Sintering Relative Grain Conductivity Activation
Temperature Density (~ size (mS/cm) energy (eV) (DFRTs) studies of LCO
(◦ C) %) (~μm)

1000 95 0.1 3 1.27

Apart from low sintering behavior, high ionic conductivity is also an
1100 98 0.3 3.68 1.19 important qualifying property of a material to qualify as a suitable
1200 99 0.4 3.55 1.20 electrolyte candidate for SOFC/SOEC applications. The information
1300 100 1.6 3.49 1.195 related to electrical conductivity of LCO and its conducting behavior
1400 100 3.1 2.42 1.192
were lacking in the literature. Studies having effect of doping of various
elements towards electrical properties of LCO is scarce. The impedance
spectroscopy is a well-established tool to characterize the electrical
parameters such as conductivity and activation energy. For impedance
studies, the LCO powder was compacted in disk form and sintered at
various temperature from 1000 to 1400 ◦ C in an interval of 100 ◦ C. The
resultant data from impedance spectra were fitted in Zsimpwin software
with the help of few common circuit elements such as R as resistance, Q
as constant phase element (CPE) to evaluate the conductivity of LCO
ceramics. The complex impedance analysis at 500 ◦ C of LCO ceramic
sintered at various temperatures (1000–1400 ◦ C) is shown in Fig. 5. In
each case, three arcs appear which corresponds to grain (high fre­
quency), grain boundary (intermediate frequency) and electrodes (low
frequency) as indicated in Fig. 5. This is very general observation for
polycrystalline ceramics, reported elsewhere [36,37]. Total conductiv­
ity of LCO was calculated according to the following formula 2:
L
σ= (2)
AR

where σ is total conductivity, A is the area of the pellet and R is the total
resistance (sum of grain and grain boundary resistance). In Fig. 5,
Fig. 5. Complex impedance spectra of LCO at 500 ◦ C sintering temperature
intercept value with real axis of sintered LCO was found to be shifting for
various temperatures.
all the cases. There is continuous shifting towards origin from high
sintered temperature to low sintered temperature except 1000 ◦ C sin­
tered sample.
Archimedes principle as tabulated in Table 2. It is clearly illustrating This indicate that conductivity of LCO increases with decrease in
that even at low temperature sintering 1000 ◦ C, LCO pellet appears to be sintering temperature from 1400-1100 ◦ C, after which conductivity
well compacted as shown in Fig. 4(a). decreases on further decreasing temperature to 1000 ◦ C. However, the
In FESEM image of 1000 ◦ C (Fig. 4(a)), a fine grains of size ~ 0.1 μm conductivity of LCO sintered at 1000 ◦ C is still higher than LCO sintered
was observed and the grain boundaries were also not clearly identifiable at 1400 ◦ C as shown in Fig. 6(a). Depending on the sintering tempera­
in comparison to other images, Fig. 4(b–e). However, all grains are well ture, conductivity of LCO varies in the range of 2.4 to 3.68 mS/cm at
compacted to each other suggesting high densification in the sample. 700 ◦ C. The properties evaluated for LCO including density, grain size,
Density >95% were also observed in density measurement for samples conductivity, activation energy are presented in Table 2. The highest
sintered at 1000 ◦ C which is consistent to FESEM observation. However conductivity of LCO measured at 700 ◦ C for samples sintered at 1100 ◦ C
Weng et al. [28] have synthesized LCO by hydrothermal route and re­ was 3.68 mS/cm whereas LCO sintered at 1400 ◦ C was showing the
ported that morphology of LCO sintered at 1500 ◦ C was open porous conductivity of approx. 2.4 mS/cm at 700 ◦ C. This may be due to either
structure. Grain boundaries started to form clearly when sintering at the higher amount of lower conducting phase of C-type [30] or higher
1100 ◦ C as shown in Fig. 4(b). Fig. 4(a–e) shown that grain growth depletion of oxygen vacancies at grain boundary core [38]. Zhang et al.
occurred when sintering temperature was increased from 1000 ◦ C to [26] found that the ionic conductivity of LCO sintered at 1500 ◦ C was
1400 ◦ C. These observations suggest that synthesis of LCO by glycine around 3 mS/cm at 800 ◦ C in dry air atmosphere which is equal to
nitrate combustion route can produce nano-particles with low conductivity of currently studied LCO when sintered at 1000 ◦ C, also in

Fig. 6. (a) Conductivity and (b)activation energy of LCO sintering temperature at various temperatures.

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B. Choudhary et al. Ceramics International xxx (xxxx) xxx

normal air atmosphere. However, few studies [30,31] have reported

higher value of conductivity as compared to our data under different
environmental conditions. The variation in conductivity of these com­
pounds when sintered at different temperature is obvious. Table 3
compares various properties of LCO available in literature with our
current work.
The Arrhenius plots of total conductivity are shown in Fig. 6(b). The
activation energy of LCO measured from the ionic conductivity is in
range of 1.19 to 1.27 eV. The activation energy of LCO sintered at 1100
◦
C exhibit lowest value of 1.19 eV while LCO sintered at 1000 ◦ C exhibit
high activation energy of 1.27 eV which is in accordance with the
conductivity data.
Recently, DFRT (ISGP) analysis has come up as a significant tool to
interpret impedance spectroscopy data. It has come up as an alternative
and advanced to equivalent circuit based fitting analysis of impedance
data [40]. DFRT analysis have gained popularity in last few years for
analysis of electrochemical processes [41], conduction mechanism [42,
43], and separating grain and grain boundary contribution [44,45]. In
this work, physical model of the system is demonstrated using ISGP Fig. 7. DFRTs spectra at 300 ◦
C (of LCO pellets sintered at various
software [46]. The reason for performing ISGP is that it not only pro­ temperatures).
vides the correct information but also grain and grain boundary
contribution can be distinguished easily, which is normally difficult to was found to be shifting towards high frequency (low tou) as shown in
analyses physically because of overlapping nature of semicircle in Fig. 8 (a) with high temperature sintered samples which is indicative for
Nyquist plots. The quality of fitting using ISGP is represented in Fig. S1 facilitation of ion transfer process i.e., faster conducting mechanism in
(supplementary) which includes normalized reproduced impedance the bulk grain.
data from ISGP (S1a), Γ vs log τ (S1b), discrepancy-complexity (S1c). Interestingly, opposite trend appeared in peak P2 shifting. P2 of
The real and imaginary parts of residuals were well below the 0.5%. DFRTs was found to be shifting towards lower frequency with increase
The normalized DFRT spectra derived from impedance data in sintering of LCOs as shown in Fig. 8(b) which may be due to slowest
(measured at 300 ◦ C of all sintered samples) can clearly distinguish the diffusion/migration of oxygen ions through grain boundary [50].
grain, grain boundary and electrode contribution as shown in Fig. 7. However, for bulk resistance calculation, this shifting of peaks limits the
Similar approach was followed in literature [46,47]. These peaks are application of DFRT techniques but resistance can be extracted from the
leveled as P1 (grain interior, i.e. bulk), P2 (grain boundary) and P3 area under the curve [44]. The activation energy (Ea) of grain and grain
(electrode contribution). To calculate the resistance, equation (3) was boundary is illustrated in Fig. 9 (calculated by ISGP). The activation
used where τo is the central peak position (time constant) of DFRT energy of bulk grain (Fig. 9(a)) was found to be in the range of
curves and Ceff is effective capacitance. 1.12–1.21 eV from temperature range of 300–600 ◦ C. Grain boundary
τo = RCeff (3) conductivity of LCO sintered at different temperature is illustrated in
Fig. 9(b), sample sintered at 1100 ◦ C was found to be low activation
The resistance was calculated by multiplying area of each peak and energy (1.32 eV) as compared to other temperature of sintering. This
maximum (un-normalized) resistivity. The effective capacitance (Ceff) of conductivity behavior may be because of different microstructure fea­
each peaks P1, P2 and P3 using ISGP were found to be of order of ~10x- tures and chemical inhomogeneous at the grain boundary that may lead
11
, ~10x-9 and ~10x-8 F cm-2 respectively, except for P2 (7.66x10-11 F to large density of blocking barrier [51,52]. The overall conductivity
cm-2) for 1000 ◦ C sintered pellets. The capacitance in the order of ~10x- calculated by impedance fitted data (by EIS fitting and ISGP) is
11
F is basically attributed to bulk grain of ionic ceramic materials [48,
49]. The resistance value, in case of 1000 ◦ C sintered pellet, of P2
(~2.95 × 105 Ω) was higher than P1 (~2.8 × 105 Ω). The grain Table 4
boundary resistance calculated by ISGP at 300 ◦ C showed that LCO Grain boundary resistance at 300 ◦ C (calculated by ISGP).
sintered at 1100 ◦ C possess lowest bulk grain and grain boundary Sintering temperature (◦ C) Rg (Ω) Rgb (Ω)
resistance as tabulated in Table 4. 1000 5.75 x10 5

Similarly, DFRTs plot (of 400 ◦ C) of all range of sintered samples is 1100 3.94x105 1.21x105
shown in Fig. 8. In this plot, two peaks (P1 and P2) are clearly visible 1200 5.74x105 1.57 x105
with effective capacitance on the order of ~10x-11 and ~10x-9 F cm-2 1300 4.65x105 3.64 x105
1400 4.05x105 4.94 x105
that corresponds to grain and grain boundary respectively. The peaks P1

Table 3
Comparison of properties of LCO with various recent literatures.
Materials Sintering Temperature (◦ C) Relative Density (~%) Grain size (~μm) Conductivity (mS/cm)@700 ◦ C Activation energy (eV) References

La2Ce2O7 1100 98 0.3 3.68 1.19 This work

1200 99 0.4 3.55 1.2
1300 100 1.6 3.49 1.195
1400 100 3.1 2.42 1.192
La2Ce2O7 1500 – – 3 (at 800◦ C) 1.112 [26]
La2Ce2O7 1500 94 10 4 – [31]
La2Ce2O7 1500 – – 4.8 – [25]
La2Ce2O7 1500 – 2.048 5.5 1.12 [39]
La2Ce2O7 1400 98 2.5 7.3 0.95 [30]
1500 100 8.5 7.8 0.98

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B. Choudhary et al. Ceramics International xxx (xxxx) xxx

Fig. 8. DFRTs spectra at 400 ◦ C (of LCO pellets sintered at various temperatures).

compared and listed in Table 5. The calculated conductivity at 600 ◦ C by observed in all the samples with a very little variation. In order to
both method (EIS fitting and ISGP) has shown the close value, for differentiate among differently sintered samples, conductivity studies
instance, total conductivity of LCO sintered at 1100 ◦ C was found to be were performed. The highest conductivity (3.68 mS/cm at 700 ◦ C in air
0.814 mS/cm by EIS fitting whereas by ISGP conductivity value at 600
◦
C was 0.803 mS/cm.
Table 5
Therefore, ISGP can be a powerful tool not only for electrochemical
Comparison of overall conductivity (by EIS fit and ISGP) of LCO sintered at 1100
processes but also provides the correct information that is embedded in ◦
C.
the data. ISGP inherently avoids overfitting as it minimizes number of
Sintering temperature Conductivity, mS/cm (EIS Conductivity, mS/cm
peaks and number of free parameters.
(◦ C) fit) (ISGP)
The possible reason for this variation in conductivity can be corre­
lated with the observed variation in microstructure i.e. grain, grain- 1000 0.555 0.524
1100 0.814 0.803
boundary size and resistance offered by grain boundary at different 1200 0.7266 0.756
sintering temperature. Also as Raman studies suggested that there is a 1300 0.734 0.738
partial interconversion of F phase to C-type phase and the amount C-
type phase structure increases with increase in sintering temperature.
Therefore the presence of both C-type and F- type phases plays a crucial atmosphere) was observed for 1100 ◦ C sintered sample, whereas 1400
role in deciding conduction behavior. Higher C or lesser F indicates less
◦
C sintered LCO was showing the conductivity of ~ 2.4 mS/cm in similar
conduction in LCO or vice versa. High temperature sintered LCO in­ measurement condition. The electrical conductivity was found to be
troduces high amount of C-type phase which may act like insulator or decreasing with increase in sintering from 1100 to 1400 ◦ C. For LCO
oxide ion trapping phase. sintered at high temperature, resistive grain boundary is contributing
The high sintering temperature may support this interconversion of more towards lowering the overall ionic conductivity of LCO. The
C-type and F- type phases at very high temperature. change in conductivity might be due to interconversion of F- type to C-
type phases at high temperature sintering and plays a crucial role in
4. Conclusions deciding conduction behavior of LCO. The presence of C- type phase in
LCO seems act like an insulator or oxide ion trapping phase. In conclu­
Nano crystalline LCO power was successfully prepared using glycine sion DFRT studies can be used a significant and well supportive tool to
nitrate combustion method. The X-Ray Diffraction (XRD) reveals that characterize the conductivity behavior of polycrystalline ceramics.
the synthesized material consists of disordered cubic fluorite-type
structure with calculated lattice parameter 5.575 Å. The radius ratio Declaration of competing interest
rA3+/rB4+ and tolerance factor for LCO was found to be 1.33 and 0.8205,
respectively which also confirms the presence of disordered phase of The authors declare that they have no known competing financial
LCO. In disordered phase, structurally LCO exhibit biphasic mixture i.e., interests or personal relationships that could have appeared to influence
C-type and F- type phases in the compound as investigated by Raman the work reported in this paper.
spectroscopy. Densification studies were done by sintering LCO pallets
at different sintering temperature. A densification of ≥95% was

Fig. 9. Activation energy of bulk grain (a) and grain boundary conductivity (b) of LCO sintered various temperatures.

7
B. Choudhary et al. Ceramics International xxx (xxxx) xxx

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