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Materials Today: Proceedings
journal homepage: www.elsevier.com/locate/matpr
Effect of Sn on the energy storage performance and electric conduction
mechanisms of BCZT ceramic
S. Belkhadir a,⇑, S. Khardazi a, D. Mezzane a,b, M. Amjoud a, O. Shapovalova c, V. Laguta d,e, I. Raevski f,
K. Pushkarova g, I. Lukyanchuk b,g, M. El Marssi b
a
IMED-Lab, Cadi-Ayyad University, Faculty of Sciences and Technology, Department of Applied Physics, Marrakech, Morocco
Laboratory of Physics of Condensed Matter (LPMC), University of Picardie Jules Verne, Scientific Pole, 33 Rue Saint-Leu, Amiens Cedex 1 80039, France
LAVQ, FCT, Universidade Nova de Lisboa, Campus de Caparica, Caparica 2829-516, Portugal
d
Institute of Physics AS CR, Cukrovarnicka 10, Prague 162 53, Czech Republic
e
Institute for Problems of Materials Science, National Ac. of Sciences, Krzhizhanovskistr. 3, Kyiv 03142, Ukraine
f
Faculty of Physics, Southern Federal University, Rostov-on-Don 344090, Russia
g
Kyiv National University of Construction And Architecture, Kyiv, Ukraine
b
c
a r t i c l e
i n f o
Article history:
Available online xxxx
a b s t r a c t
The B-site-doping method of barium titanate (BaTiO3) is one of the promising route to prepare lead-free
materials with enhanced dielectric and piezoelectric properties. Lead-free (Ba0.85 Ca0.15)(Zr0.1-xSnxTi0.9)O3
[BCZT:Sn] (x = 0, 0.02, 0.04 and 0.06) ceramics were synthesized using the sol-gel method. The effects of
Sn content on the energy-storage performance and electric conduction mechanisms of BCZT ceramic
were systematically investigated. The energy storage performance investigation showed that the recoverable energy storage has been enhanced with Sn doping rate, the composition doped x = 0.02 (BCZT:
2Sn) depicted the highest recoverable energy density and efficiency (Wrec = 19 mJ/cm3, ɳ = 81.65%).
The electrical properties of the BCZT:Sn ceramics were investigated using the impedance spectroscopy
technique at temperature range of 25–450 °C. The net impedance of the samples showed a significant
enhancement as the Sn content increases, owing to the lattice distortion created by the relative difference
in the radius of Sn4+and Zr4+ and different outer electronic shells. The AC conductivity was measured and
analyzed as a function of frequency and temperature. Obtained activation energy values were associated
with possible conduction mechanisms.
Ó 2021 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the International Conference on Phosphates (ICP): Fundamentals, Processes and Technologies.
1. Introduction
Barium titanate (BaTiO3 or BT)- based materials have been
intensively studied for their interesting electrical properties for
instance low dielectric loss, high dielectric constant, and ferroelectric behavior. The ferroelectric materials derived from BT have
been used for an immense range of applications in electronic
devices, functioning as pulse generating devices, multilayer ceramic capacitors, actuators, infrared detectors, voltage tunable
devices in microwave electronics, and charge storage devices [1,2].
Doping of ferroelectric can be used as an effective strategy to
tune several functional properties. It has been found that doping
⇑ Corresponding author.
E-mail address: saad.belkhadir@edu.uca.ac.ma (S. Belkhadir).
BT with different dopants could extremely contribute to the
enhancement of the piezoelectric and dielectric properties. For
instance it has been reported that doping of BT with Ca2+ and
Zr4+ (BaTiO3-CaTiO3-BaZrO3 solid solutions) lead to dramatically
enhanced piezoelectric properties (d33 620pC/N) with relatively
low Curie temperature (TC 93 °C) for xBa(Zr0.2Ti0.8)O3–(1-x)
(Ba0.7Ca0.3)TiO3 (x = 0.5) (BCZT) composition [3].
It should be pointed out that the electrical properties of ceramics fabricated by the solid-state method, are sensitive to the sintering conditions [4–6]. Moreover, high sintering temperature
generally contributes to the formation of impurity phases and a
large value of the dielectric loss, which is considered as imperfection in the majority of electronic applications [4]. On the other
hand, BCZT ceramics synthesized by wet chemical techniques for
instance sol–gel method depicted an excellent electrical
https://doi.org/10.1016/j.matpr.2021.05.517
2214-7853/Ó 2021 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the International Conference on Phosphates (ICP): Fundamentals, Processes and Technologies.
Please cite this article as: S. Belkhadir, S. Khardazi, D. Mezzane et al., Effect of Sn on the energy storage performance and electric conduction mechanisms of
BCZT ceramic, Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2021.05.517
S. Belkhadir, S. Khardazi, D. Mezzane et al.
Materials Today: Proceedings xxx (xxxx) xxx
ranging from 25 °C to 450 °C by using a precision HP 4284A LCR
Meter. The function of measure was Cp-D with an applied voltage
of 0.5 V.
performance compared to the ceramics prepared by the solid-state
method due to the good stoichiometric composition of the resultant phase, nanoparticle sizes control, reduction in the processing
temperatures and the chemical purity [7].
Many research groups have reported the beneficial effect of Sn4+
on enhancing the dielectric properties, the diffuse phase transition,
the electrocaloric and energy storage properties of BCZT ceramics
[8]. Also it is worth to mention that the ferroelectric–paraelectric
(FE– PE) phase could be shifted towards room temperature as
Sn4+ ion dopant content increases in BCZT [9–15]. Mondal et al
have reported that the lattice distortion created by the relative difference in the radius of Ca2+ and Ba2+ ions in Ba1-xCaxZr0.1Ti0.9O3
(BCZT) system resulted in the enhancement in the grain boundary
resistivity of the Ca doped BZT [16].
In this study, we investigate the effect of Sn substitution on the
energy storage performance, and conduction mechanism of (Ba0.85Ca0.15) (Zr0.1-x Snx Ti0.9)O3(x = 0, 0.02, 0.04, and 0.06) ceramics.
3. Energy storage performance
Energy storage referring to the capture of energy generated at
one time and consumed at a later time. In the case of nonlinear
dielectrics, the energy storage performances such as total energy
density (Wtot), recoverable energy density (Wrec), and energy storage efficiency (ɳ) could be determined using the following
equations:
Z
Pmax
EdP
ð1Þ
EdP
ð2Þ
0
Z
Pmax
Pr
2. Experimental section
Wrec
Wrec
*100 ¼ WrecþWloss
* 100 (3)where Pmax, Pr, E, Wtot, Wrec, Wloss,
Wtot
and ɳ described as maximum polarization, remnant polarization,
applied external electric field strength, total energy density, recoverable energy density, loss energy density, and energy storage efficiency respectively.
Fig. 1(a-d) exhibits the polarization–electric field (P–E) hysteresis loops of the BCZT ceramics with increasing temperature from
25 to 120 °C under an electrical field of 12 kV/cm amplitude. It
(Ba0.85 Ca0.15) (Zr0.1-x Snx Ti0.9) O3 (x = 0, 0.02, 0.04, and 0.06)
ceramics were prepared by employing the sol–gel method as we
reported previously [8,17]. The resulting powders were calcined
at 1000 °C for 4 h. Then, the pellets pressed at 2.5 ton /cm2 were
sintered at 1350 °C for 2 h.
The complex impedance of the sintered ceramics was measured
in the frequency range from 20 Hz to 1 MHz and the temperature
Fig. 1. P–E loops of BCZT ceramics as a function of temperature for Sn concentration (a) x = 0, (b) x = 0.02, (c) x = 0.04, and (d) x = 0.06.
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S. Belkhadir, S. Khardazi, D. Mezzane et al.
Fig. 2. Electric-field-related and the temperature-related showed energy-storage properties of (Ba0.85 Ca0.15) (Zr0.1-xSnxTi0.9) O3 (a) x = 0, (b) x = 0.02, (c) x = 0.04, and (d)
x = 0.06.
Fig. 3. Energy-storage properties of the BCZT-Sn samples.
Fig. 4. P-E loop for BCZT:2Sn at 120 °C.
can be seen that all samples exhibit well visible hysteresis loops. Pr
rises sharply initially until near phase transition temperature, and
then decreases sharply for all samples.
Fig. 2 (a-d) depicts the variation of Wrec, Wloss, and ɳ of Sn doped
BCZT with temperature, it can be seen that the corresponding ɳ
values are considerably affected as the temperature increased.
Fig. 2 indicates that the energy storage density increases as a function of the Sn content, The BCZT:2Sn shows the highest recoverable
energy density and efficiency (Wrec = 19 mJ/cm3 at 12 kV/cm and ɳ
80%) at 120 °C as illustrated in Fig. 3. This could be attributed to
the slim hysteresis loop behavior, which allows a high PS and low
EC values [18].The enchancement of the recoverable energy density
and efficiency as a function of Sn could be due to the increase of the
grain size growth as shown in our previous work [8] since the
increase in the grain size is followed by an easier domain wall rotation due to the raise of the domain switchability [19] hence the Sn
affected the ferroelectric properties which influences the energy
storage performance. Furthermore we observed a discontinuity in
slope at 40–50 °C and 120 °C, which could reflect the diffuse
FE-PE phase transition , in the region of this diffuse phase transi3
S. Belkhadir, S. Khardazi, D. Mezzane et al.
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Fig. 5. Frequency dependence of the real part of impedance (Z’) for (Ba0.85 Ca0.15) (Zr0.1-xSnxTi0.9)O3 ((a) x = 0, (b) x = 0.02, (c) x = 0.04, and (d) x = 0.06) at different
temperatures.
efficiency (ɳ) behavior; similar results have been found in literature [20].Fig. 4.
4. Complex impedance spectroscopy
The electrical properties of the Sn doped BCZT ceramics have
been investigated using complex impedance spectroscopy (CIS).
It is a commonly used method to analyze the electrical properties
of the polycrystalline materials. The measurement of the resistance
and capacistance as a fuction of frequency and temperature allows
to differentiate between the grains and grain boundaries distributions. Data can be presented through electrical impedance Z*, electric modulus M*, and dielectric permittivity e* which can be
expressed by the following relation (4) [17]:
M ¼ jxC 0 Z ¼
1
e
x ¼ 2pf is
ð4Þ
With
angular frequency, C0 = e0 A/d is the vacuum
capacitance of the cell, e0 = 8.85 10-12F/m is the vacuum permittivity, A and d are the area and thickness of the sample
respectively.
Fig. 5. (a–d) shows the variation of the real part of impedance
(Z0 ) as a function of frequency for (Ba0.85Ca0.15)(Zr0.1-xSnxTi0.9)O3
Fig. 6. Frequency dependence of the real part of impedance at 400 °C for
compositions with different Sn content.
tion i.e. in a rather wide temperature range the fluctuations of the
dipoles increase substantially which influence the energy storage
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Fig. 7. Variation of the imaginary part of impedance (Z00 ) with frequency at different temperatures for (Ba0.85Ca0.15)(Zr0.1-xSnxTi0.9)O3 ceramics (a) x = 0, (b) x = 0.02, (c)
x = 0.04, and (d) x = 0.06.
tance (NTCR) type behavior of the material [21,22]. The variation of
Z ’ shows a strong dispersion followed by a plateau behavior for
low frequencies region, followed by a merging for all temperatures
involving the absence of space charge polarization at highfrequency regions [21,23]. Furthermore, in general, the (Z0 )
response should depict two plateau regions attributed to the grain
and grain boundary contribution. In a different manner, our study
for the real part of impedance (Z0 ) only showed one plateau at low
frequency, which means that the observed low-frequency plateau
is mainly attributed to the grain boundary contribution. Furthermore, Fig. 6 shows the variation of the real part of impedance
(Z0 ) as a function of x , and one can clearly see that the grain boundary resistance is enhanced by increasing the Sn4+ content in the
(Ba0.85 Ca0.15) (Zr0.1Ti0.9)O3 system.
Fig. 7 (a–d) illustrates the frequency dependence of the imaginary part of impedance (Z00 ) at different temperatures for (Ba0.85Ca0.15)(Zr0.1-xSnxTi0.9)O3 (x = 0, 0.02, 0.04, 0.06) ceramics. The Z00
response is mainly characterized by two relaxation peaks attributed to the grain boundaries at the low-frequency region and grains
at high frequencies. One can also notice that the Z00 values at high
frequencies for all temperatures follow straight line in the logarithmic scale and merge in the high-frequency region showing a
temperature-independent behavior.
In addition, the peaks of the imaginary part of impedance (Z00 )
become higher and shift towards the lower frequency region when
the Sn4+ concentration increases as is illustrated in Fig. 8. This
Fig. 8. Frequency dependence of the imaginary part of impedance at 400 °C for
compositions with different Sn content.
(x = 0, 0.02, 0.04, and 0.06) ceramics at different temperatures. The
decreasing nature in the magnitude of Z0 with increasing temperature suggests the typical negative temperature coefficient of resis5
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Fig. 9. Nyquist plot at various temperatures along with the fitting results for (Ba0.85Ca0.15)(Ti0.9Zr0.1-xSnx)O3 ceramics at different temperatures (a) x = 0, (b) x = 0.02, (c)
x = 0.04 and (d) x = 0.06.
phase element. The resistance R, and capacitance Q for grain and
grain boundaries at 340 °C are shown in Table 1.
It appears clear that the substitution by Sn4+ at the octahedral B
site of BCZT increases dramatically the resistivity of the BCZT
ceramics. Obviously, the substitution of Sn4+ with a smaller radius
for the larger Zr4+ leads to the shrinkage of the lattice of BCZT
which makes the Ti-O bond stronger [24], which could diminish
the oxygen vacancies mobility. Besides, the outer electronic shells
of the Sn and Zr (Ti) are different: 5s25p2 and 4d25s2 (3d24s2),
respectively, that leads to different Me- O covalent bonds. All this
changes both the ionization energies of charged oxygen vacancies
(F and F+ centers [25]) and oxygen vacancy mobility, thus may
induce an increase of the resistance of the grain and grain boundary [16].
Table.1
Resistance, capacitance values determined for grain and grain boundary at 340 °C.
composition
Rg (X)
Qg (F)
Rgb(X)
Qgb(F)
BCZT
BCZT:2Sn
BCZT:4Sn
BCZT:6Sn
18,675
63,963
163,030
244,510
1.346E-9
1.194E-10
2.048E-10
5.651E-11
43,222
246,780
400,210
389,460
1.5602E-7
2.1996E-8
7.407E-9
3.242E-9
behavior could indicate that the hopping mobility of charge carriers become slower both inside the grains and at the grain boundaries with the increase in Sn content [16].
5. The Nyquist diagram
6. AC conductivity analysis
Fig. 9(a-d) represents the Nyquist plots for the (Ba0.85Ca0.15)
(Zr0.1-xSnxTi0.9)O3 ceramics for several temperature from the
300 °C to 400 °C range. It is clearly seen that all the samples show
two semi-circles in the Nyquist plot which suggest that the polarization response in our system is due to the grain and grain boundary contributions. We also noticed that the heights of the semicircles for both grain and grain boundary become smaller with
increasing temperature. For both semi-circles, the grain and grain
boundary can be represented by an equivalent electric circuit
shown in the inset of Fig. 9 (b) where CPE denotes the constant
Fig. 10 (a-d) depicts the electrical conductivity vs. frequency at
different temperatures for (Ba0.85Ca0.15)(Ti0.9Zr0.1-xSnx)O3 ceramics.
The nature of the variation of r with temperature indicates that
the character of the dispersion phenomenon of conductivity
appears both in the low as well as in the high-frequency region.
At higher temperatures, the low-frequency conductivity may be
approximated to the dc conductivity (rdc), and the highfrequency region corresponds to the ac conductivity (rac) for all
samples. The conductivity spectrum can be divided into three
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Fig. 10. The frequency dependent ac-conductivity r for (Ba0.85Ca0.15)(Ti0.9Zr0.1-xSnx)O3 ceramics at different temperatures (a) x = 0, (b) x = 0.02, (c) x = 0.04, (d) x = 0.06.
five main regions as shown in Fig. 12.(a), three ferroelectric regions
nominated as FEI, FEII, and FEIII as well as two paraelectric regions
designated by PEI and PE II. On the contrary, the doped ceramics,
(Ba0.85Ca0.15)(Ti0.9Zr0.1-xSnx)O3 (x = 0.02,0.04 and 0.06) show only
two ferroelectric regions FEII and FEIII.This can be justified by
the co-existence of the orthorhombic-tetragonal phase at room
temperature for the undoped ceramic which manifests as a ferroelectric region as we have shown in our previous work [8].
Every region is characterized by different slopes of the lnrac(T1) revealing the presence of different conduction mechanisms
combined with their corresponding values of activation energy
(Ea). The values of Ea were calculated assuming an Arrhenius
behavior law for charged particles hopping according to the equation (5) [28].
regions: the low frequency (dc) plateau regime (I in Fig. 11.
Intermediate-frequency dispersive regime and high-frequency plateau regime (II and III in Fig. 11. These aspects can be explained by
the jump-ion (or jump-charge) relaxation model[26] . In the low
frequency regime, the weak ac electric field cannot disturb the
hopping conduction mechanism of the charged particles, conductance may be well approximated to the dc value. The charged carriers hop from one localized site to its neighboring vacant site due
to the available long time period; such successive jumps result in a
long-range translational motion of ions contributing to dc conductivity. However, at higher frequencies, two relaxation processes
took place : unsuccessful hopping in which the hopping ion jumps
back to its initial position and is described as the forward–backward hopping process, and successful hopping wherein the neighborhood ions become relaxed and the hopping ion stays at the new
site. The high and constant hopping conductivity in the highfrequency plateau regime is due to the contribution of every individual hop when the time is sufficiently short. In the intermediatefrequency regime, the dispersive conductivity is explained with the
increase in the ratio of successful to unsuccessful hopping [27].
The ac conductivity behavior of the ceramics as a function of
temperature is depicted in Fig. 11 (a-d). We notice that the ac conductivity increases with an increase of frequency, especially at low
temperatures. The ac conductivity-temperature plots for the
undoped ceramic (Ba0.85Ca0.15)(Ti0.9Zr0.1)O3 can be separated into
Ea
kb T
rac ¼ r0 exp
ð5Þ
here rac is the ac conductivity, r0 represents the pre-exponential
term, Ea is the activation energy, kb is the Boltzmann constant,
and T is the temperature in Kelvin scale.
The activation energies determined from the temperature
response of ac conductivity at 1 kHz and 10 kHz for all samples
are listed in Table 2.
The Ea values in the FE II region for all samples are in the range
0.08–0.16 eV as a result of the hopping of electrons or holes[29] .
7
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Fig. 11. Variation of ac conductivity as a function of temperature for (Ba0.85Ca0.15)(Zr0.1-xSnxTi0.9)O3 ceramics (a) x = 0, (b) x = 0.02, (c) x = 0.04, and (d) x = 0.06.
Table.2
Activation energy values Ea in eV for ac conduction obtained from the different regions of temperature dependent ac conductivity at 1 kHz and 10 kHz.
Ea (eV)
x=0
x = 0.02
x = 0.04
x = 0.06
FEI
FEII
FEIII
PEII
0.53
–
–
–
0.09
0.08
0.16
0.08
0.38
0.34
0.21
0.42
0.94
0.70
0.60
0.69
effect [32,33] to the observed decrease of conductivity above TC.
Though this effect is usually studied in highly-conductive ferroelectrics [32,33] it is often observed in ferroelectric ceramics with
rather low conductivity [34,35]. At high temperatures, the evaluated Ea values for the PEII region are in the range 0.60–0.94 eV
being very close to the values associated with the hopping of double ionized oxygen vacancies (V :: O ) reported for other perovskite
oxides [27,36–38].
Differently, for the FE III region, the activation energy values manifest in the range 0.21–0.42 eV which indicates conduction by
phonon-assisted electron/hole hopping [29]. It is worth noting that
these values of Ea correspond well to the energy of the first (several
hundredth of eV) and the second (several tenth of eV) levels of the
oxygen vacancy determined both theoretically and experimentally
for a large number of perovskite oxides. (see, e.g., Ref.[30] and references therein).
A dramatic decrease of conductivity in the PEI region, i.e. just
above TC, seems to be caused by the lowering of the hopping
mobility of charge carriers in the vicinity of the diffused phase
transition due to fluctuations of polarization [31]. However in view
of the established difference in the conductivity values in the grain
bulk and at the grain boundaries, one cannot exclude the contribution of the Positive Temperature Coefficient of Resistivity (PTCR)
7. Conclusions
Lead-free (Ba0.85 Ca0.15) (Zr0.1-xSnxTi0.9) O3 (x = 0,0.02, 0.04 and
0.06) ceramics were prepared by sol–gel method , the effect of
Sn on the energy storage performance and conduction mechanisms
was studied systematically.
8
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S. Belkhadir, S. Khardazi, D. Mezzane et al.
The highest recoverable energy density and efficiency were
found for x = 0.02 of Sn (BCZT:Sn 2) composition (Wrec = 19 mJ/
cm3 at 12 kV/cm and ɳ of 81.65%).
The prominent effect of Sn substitution on the electric properties of the ceramics was revealed. In particular, the net impedance
of the grain and grain boundaries has increased as a function of Sn
substitution. This behavior is interpreted as due to the large difference in the ionic radii of Sn4+ and Zr4+ and different covalent
bonds: Sn(5 s) -O(2p) and Zr(4d) or Ti(3d) -O(2p), respectively
resulting in the shrinkage of the lattice, change of the Me - O bonding and activation energies for release of trapped electrons from
oxygen vacancies and oxygen vacancies mobility. All these factors
will essentially influence the grain and grain boundary resistance.
The conductivity as a function of frequency and temperature
has revealed the existence of three main regimes at low, intermediate, and at high frequencies. The appearance of these regions is
explained in the frame of the jump relaxation model.
The analysis of the conductivity as a function of temperature
has distinguished three temperature regions in the ferroelectric
phase for the undoped ceramic(x = 0) and only two for the doped
ceramics(x = 0.02, 0.04 and 0.06) where the temperature coefficient of conductivity changes the sign.
[7]
[8]
[9]
[10]
[11]
[12]
[13]
CRediT authorship contribution statement
[14]
S. Belkhadir: Investigation, Writing - original draft, Visualization. S. Khardazi: Investigation. D. Mezzane: Conceptualization,
Validation, Resources, Supervision. M. Amjoud: Conceptualization,
Validation, Resources, Supervision. O. Shapovalova: Formal analysis, Resources. V. Laguta: Investigation. I. Raevski: Investigation. K.
Pushkarova: Formal analysis, Resources. I. Lukyanchuk: Formal
analysis, Resources. M. El Marssi: Formal analysis, Resources.
[15]
[16]
Declaration of Competing Interest
[17]
The authors declare that they have no known competing financial interests or personal relationships that could have appeared
to influence the work reported in this paper.
[18]
Acknowledgements
[19]
The authors gratefully acknowledge the financial support of
CNRST Priority Program PPR 15/2015 and the European H2020MSCA-RISE-2017-ENGIMA action. IR acknowledges a support from
the Ministry of Science and Higher Education of the Russian Federation [State task in the field of scientific activity, scientific project
No. 0852-2020-0032 (BAS0110/20-3-08IF)].
[20]
[21]
[22]
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