J Electroceram

DOI 10.1007/s10832-017-0074-1

Synthesis and characterizations of SrTiO3 modified BNT-KNN

ceramics for energy storage applications
M. Chandrasekhar 1 & P. Kumar 1

Received: 21 September 2016 / Accepted: 14 February 2017

# Springer Science+Business Media New York 2017

Abstract Lead-free (1-x) [0.934BNT-0.07KNN]-x SrTiO3/ high dielectric constant (ε r ) and comparatively fast
BNT-KNN-ST ceramics with x = 0, 0.04, 0.08, 0.12 and discharging speed of ferroelectric (FE) materials make them
0.16 were synthesized in single perovskite phase by conven- suitable for high energy storage density applications [1].
tional solid state reaction route. Effect of SrTiO3 modification Energy storage density (W1) of a FE material can be calculated
on phase, microstructure, dielectric, electric field induced po- from its polarization vs. electric field (P-E) hysteresis loop by
larization, electric field induced strain and energy-storage using the following relation:
properties were investigated and discussed in detail. Pmax
Dielectric study confirmed relaxor nature with a drastic de- W 1 ¼ ∫ E dP ð1Þ
crease of Tc with the increase of SrTiO3 content in BNT-KNN- 0
ST system. Saturation polarization, remnant polarization, co-
ercive field (Ec) and maximum induced strain decreased with where, E is the applied electric field and P is the polarization.
the increase of SrTiO3 content in BNT-KNN-ST system. High Energy storage efficiency (η) of a FE material is calculated by
recoverable energy storage density of ~0.59 J/cm3 with energy using the following relation:
storage efficiency of ~64% were obtained in x = 0.16 ceramic .
samples, which suggested its usefulness for energy-storage η ¼ W 1 ðW 1 þ W 2 Þ ð2Þ
capacitor applications.
where, W1 is the stored energy density; W2 is the energy loss
density [2, 3]. Equations 1 & 2 suggest that FE materials with
Keywords Energy-storage . Relaxor . Microstructure .
slim P-E loops, high saturated polarizations (Ps) and low rem-
Polarization
nant polarizations (Pr) would exhibit high energy storage den-
sity. There are two ways to achieve slim P-E loop, high Ps and
low Pr in a FE material. These two methods are: (i) to modify
1 Introduction FE material, having large energy storage density, with a suit-
able antiferroelectric (AFE) material [4] and (ii) to search for
Recently, due to environmental concerns, green energy stor- an effective relaxor FE material [5]. Liu et al. [6, 7] studied the
age materials and devices are attracting the attention of re- temperature dependence of dielectric and energy storage prop-
search community. In comparison to Lithium based batteries, erties of lead based antiferroelectric (AFE) ceramics. Due to
environmental concerns of lead based materials, there is a
need to develop lead free ceramics for energy storage appli-
cations. Among the potential lead free FE materials for high
energy storage density applications, Bi0.5Na0.5TiO3 (BNT)-
* P. Kumar
pvn77@rediffmail.com; pawankumar@nitrkl.ac.in based complex FE materials are the promising materials.
BNT has a rhombohedral perovskite structure with R3C sym-
1
Department of Physics & Astronomy, NIT Rourkela, Odisha 769008, metry. In the BNT-based system, A-site in the perovskite unit
India cell is shared by mixed-valency ions like: Bi3+, Na+, K+, Sr2+
 J Electroceram

etc. Local interactions among A-site ions in BNT based sys- hydraulic press with 6 tons/cm2 pressure for 3 min.
tems can give rise to multiple phase transitions [8]. These green pellets were sintered in air atmosphere at
Bi0.5Na0.5TiO3 – K0.5Na0.5NbO3 (BNT-KNN) is one of the 1100 °C for 4 h. Retention of single perovskite phase in
BNT-based system having mixed-valency ions at A-site. It is sintered ceramic samples was confirmed by XRD study.
a known fact that a FE system exhibit optimum performance Surface microstructures of the pellets (as sintered) were
near its morphotropic phase boundary (MPB) compositions. observed using Field emission scanning electron micro-
Kounga et al. [9] and Chandrasekhar et al. [10] reported the scope (NOVA nano SEM). Polished sintered pellets
existence of a MPB with rhombohedral and tetragonal phases were coated with silver paste and fired at 400 °C for
in the 0.93BNT-0.07KNN composition. This MPB composi- 30 min for good adhesion. Dielectric constant (εr) and
tion exhibits good FE property and large electric field induced dielectric loss (tanδ) were measured as a function of
strain. Among the RT non-polar materials, SrTiO3 (ST) is an temperature using a computer interfaced HIOKI 3532–
important perovskite cubic system. Good breakdown strength 50 LCR-HITESTER. Polarizations vs. electric field (P-
with linear dielectricity of ST system accounts for its low E) hysteresis loops at room temperature were measured
energy dissipation and suitability for energy storage applica- using Radiant precision premier II. Strain vs. electric
tions [11]. field (S-E) hysteresis loops were measured using MTI-
Therefore, in the present work, for obtaining slim P-E 2100 Fotonic sensor, attached with Radiant precision
loops, high Ps and low Pr, 0.93BNT-0.07KNN composition premier II unit.
is modified with ST system. Phase formation, dielectric, FE
and energy-storage properties of the ST modified BNT-KNN
ceramics were studied and discussed in detail.
3 Results and discussion

3.1 XRD and microstructure study

2 Experimental details
Figure 1 shows the XRD patterns of sintered BNT-KNN-ST
Conventional solid-state reaction route was followed to syn- ceramic samples. Single perovskite phase is observed in all the
thesize (1-x) [0.93BNT-0.07KNN]-x SrTiO3 (BNT-KNN-ST) compositions. Fig. 1(b), (c) show the enlarged pictures of
ceramic samples with x = 0, 0.04, 0.08, 0.12 and 0.16. (111) and (200) XRD peaks. Splitting of (111) and (200)
Stoichiometric weights of Bi2O3, Na2CO3, TiO2, SrCO3, XRD peaks of x = 0 ceramic samples suggests its MPB nature.
Nb2O5 and K2CO3 (all are 99.9% purity) precursors were ball In x = 0 ceramic samples, rhombohedral (R) and tetragonal (T)
milled for 20 h (h) by using zirconia balls with acetone as phases with lattice parameters: (aR, αR) ~ (5.4974 Å, 90.08°)
grinding media followed by calcination at 850 °C for 4 h. and (aT, cT) ~ (5.4998 Å, 13.7274 Å), respectively [9, 10] were
Single perovskite phase formation in calcined powders obtained. In other than x = 0 ceramic samples, XRD peak
was confirmed by X-ray diffraction (XRD) (Rigaku splitting corresponding to (111) and (200) planes is not ob-
Ultima IV X-ray diffractometer, Tokyo, Japan) tech- served, which suggests cubic or pseudo cubic structures of
nique. Green pellets of ~10 mm in diameter and these samples [12]. In x = 0.04, 0.08, 0.12 and 0.16 ceramic
~1.5 mm in thickness were compacted using a uniaxial samples, cubic lattice parameters ~3.8608 Å, 3.8638 Å,

Fig. 1 XRD patterns of the BNT-

KNN-ST ceramic samples
J Electroceram

Fig. 2 FESEM micrographs of

the BNT-KNN-ST ceramic
samples

3.8641 Å and 3.8686 Å, respectively were obtained. Figure 2 shows the FESEM micrographs of sintered
With the increase of ST content, XRD peaks shift to- BNT-KNN-ST ceramic samples. Average grain size of
wards higher angle side, shown in Fig. 1(b). This sug- BNT-KNN-ST ceramic samples, determined by using
gests the decrease of lattice parameters with the increase linear intercept method, are given in Table 1. With the
of ST content [12]. increase of ST content from x = 0 to 0.08, average

Table 1 Dielectric (at1kHz), ferroelectric, energy storage and induced strain properties of BNT-KNN-ST ceramic samples

Sample G εr(RT) εm Td (°C) Tc (°C) Ec Pr (μC/cm2) Ps (μC/cm2) W1 (J/cm3) η% S%

(μm) (kV/cm)

x=0 1.15 945 2666 145 280 25.7 21.2 31.7 0.19 6.6 0.62
x = 0.04 1.58 1258 2498 123 270 21.5 9.4 20.5 0.25 13.5 0.18
x = 0.08 1.68 1626 2645 116 259 8 3.2 21.2 0.5 42.8 0.15
x = 0.12 1.60 1652 2566 107 230 4.7 1.9 21.6 0.58 52.1 0.11
x = 0.16 0.59 2030 2526 90 206 2.8 1.2 20.6 0.59 64.2 0.09
 J Electroceram

Fig. 3 Dielectric spectra of the BNT-KNN-ST ceramic samples

grain size increases and above x = 0.08, average grain presence of aliovalency at A-site ions and covalency of
size starts decreasing. It is observed from microstructure A-O bond in BNT-KNN-ST ceramic samples. During
that tightly bounded sharp cornered cubic like grains are sintering process, mass transfer increases with the in-
present in x = 0 ceramic samples and porosity increases crease of diffusion of single-ion-defects, which can pro-
with the increase of ST content in BNT-KNN-ST ceram- mote the grain growth. This suggests that upto
ic samples. Variation of grain size can be explained on x = 0.08, diffusion of single-ion defects process domi-
the basis of complex defects theory. Complex defects as nates and diffusion process of complex defects starts
well as single-ion vacancies can be formed due to the dominating in x = 0.12 and 0.16 ceramic samples [13].
J Electroceram

Fig. 4 1/εr vs. T plots of the BNT-KNN-ST ceramic samples

3.2 Dielectric properties: nature, while Bi–O bonds are covalent in nature. Increased
dielectric dispersion with the increase of ST content can be
Fig. 3 shows temperature dependence of εr and tanδ at differ- explained in terms of increased heterogeneity at A-site. This
ent frequencies of sintered BNT-KNN-ST ceramic samples. heterogeneity can perturb the Coulombic interaction at long
Dielectric anomaly, observed near depolarization temperature range and can ultimately lead to the formation of polar nano-
(Td), corresponds to FE to intermediate phase transition. FE- domains. Moreover, increased heterogeneity at A-site reduces
AFE phases coexist beyond Td. Whereas, dielectric anomaly, the degree of coupling between permanent dipoles, which
observed near maximum dielectric constant temperature (Tm results in destruction of FE domains with short-range cation
or Tc) corresponds to paraelectric phase transition [2, 14]. Up ordering and can lead to relaxor behaviour [15]. At high tem-
to Tc/Tm, value of εr at different frequencies increases with the perature, dielectric loss at lower frequencies increases drasti-
increase of temperature which can be related to the increase in cally, which can be accounted by the increased electrical con-
polarization due to increased easy orientation of dipoles. ductivity of space charges [16]. RT dielectric constant in-
Above Tc/Tm, εr decreases due to increase of thermal oscilla- creases with the increase of ST content, which may be due
tion of molecules and increase of degree of disorderness of to the increase of space charge effect as well as compositional
dipoles. Dielectric parameters such as εr , εm, Td and Tm are inhomogeneity [17]. Decrement in Td with the increase of ST
given in Table 1. With the increase of ST content, Tm decreases content is caused by increased AFE ordering in the BNT-
and dielectric spectra broadens, which is attributed to the in- KNN-ST system [18].
creased isovalency of A-site and increased covalency of A–O Curie–Weiss temperature (TCW) of BNT-KNN-ST ceramic
bond in the BNT-KNN-ST system. This increased isovalency samples is calculated from linearly fitted graph between 1/εr
can be accounted in terms of partial replacement of (Bi3+/Na+/ vs. T for T > Tm. Burn’s temperature (above Tc) TB, below
K+) ions by Sr2+ ions at A-site. Increased covalency of A–O which 1/εr is a non-linear function of T is determined from 1/εr
bonds can be accounted in terms of fractional replacement of vs. T graph, shown in Fig. 4. TB values ~302, 295, 294, 267 and
Na–O or K–O bonds by Sr–O bonds, since they are ionic in 260 °C were obtained for x = 0, 0.04, 0.08, 0.12 and 0.16 ceramic
 J Electroceram

samples, respectively. TB represents cross-line between soft mode materials, respectively [22]. Figure 5 shows the log (1/εr – 1/
and order–disorder dynamics. Therefore, when T < TB, polar εm) vs. log (T − Tm) plots of the BNT-KNN-ST ceramic sam-
nano-regions appear, and the displacive-type soft mode is over ples. Slopes of the linearly fitted lines in log (1/εr – 1/εm) vs.
damped [19] and Curie–Weiss law becomes invalid within the log (T − Tm) plots gives γ factor. γ values ~1.94, 1.78, 1.74,
Tm–TB temperature range. ΔTm = Tm -TB, estimates the deviation 1.89 and 1.97 are observed for x = 0, 0.04, 0.08, 0.12 and 0.16
from classic Curie–Weiss behaviour of a system. Non-zero values ceramic samples, respectively. γ values of BNT-KNN-ST ce-
of ΔTm suggest the relaxation near phase transition and broaden- ramic samples are ~2, which confirm their diffusive phase
ing in the εr vs. T plots [19, 20]. transition nature.
Diffuseness of BNT-KNN-ST ceramic samples is studied
by plotting dielectric vs. temperature behaviour near Tc of the 3.3 P-E hysteresis loop and energy storage density study
modified Curie–Weiss law [1, 21], given below:

ð1=εr Þ−ð1=εm Þ ¼ ðT −T m Þγ =C ð3Þ Figure 6 shows the P-E hysteresis loops, measured at 10 Hz
frequency, of BNT-KNN-ST ceramic samples. A well saturat-
where γ and C are constants. Normally, γ value is between 1 ed typical P-E hysteresis loop of x = 0 ceramic sample con-
and 2 and gives information about the nature of phase transi- firms its FE nature. Whereas, with the increase of ST content,
tion. γ values are 1 and 2 for normal FE and ideal relaxor FE a drastic reduction in Ec and Pr values with relatively less

Fig. 5 log (1/εr – 1/εm) vs. log (T − Tm) plots of the BNT-KNN-ST ceramic samples
J Electroceram

reduction in Ps values is observed, which suggests the sup-

pressing of FE order and increase of non-polar order [23].
Variation of W1 and η% with the increase of ST content in
BNT-KNN-ST ceramic samples is shown in Fig. 7. All the
measurements for W1 and η% are done under same external
applied electric field (~70 kV/cm). With the increase of ST
content, W1 and η% increases, which can be related to
increase of non-polar state and decrease of FE state in
BNT-KNN-ST system [9, 24]. Enhancement of W 1
values with the increase of ST content can also be fur-
ther related to reduction in remnant polarization [25],
confirmed by P-E hysteresis loop study. Highest W1
value of ~0.59 J/cm3 as well as highest η% value of
~64 was obtained in x = 0.16 ceramic samples, which
Fig. 7 Variation of W1 and η% with ST content of the BNT-KNN-ST
suggest its usefulness for energy storage applications.
ceramic samples

4 Conclusions
3.4 S-E hysteresis loop study
XRD study confirmed rhombohedral-tetragonal MPB nature
Figure 8 shows the RT bipolar S-E hysteresis loops,
of x = 0 ceramic samples and pseudo cubic structure nature of
measured at 10 Hz, of BNT-KNN-ST ceramic samples.
other ceramic samples. Variation of average grain size with ST
Butterfly shaped S-E loop of x = 0 ceramic samples
modification in BNT-KNN-ST system was explained on the
suggest its piezoelectric and FE nature. Whereas, de-
basis of complex defect theory. Dielectric study and modified
crease of butterfly nature of S-E loops with the increase
Curie–Weiss law revealed relaxor behaviour of ST modified
of ST content suggest the decrease of piezoelectric na-
BNT-KNN-ST ceramic samples. Drastic decrease of Pr, Ec
ture and increase of AFE nature [2, 26]. Asymmetry in
and S% with the increase of ST content suggested the in-
butterfly S-E hysteresis loops of x = 0 and 0.04 ceramic
creased AFE nature of BNT-KNN-ST ceramic samples.
samples suggest the presence of internal bias, resulting
Highest values of W1 ~ 0.59 J/cm3 and η% ~64 of x = 0.16
from volatilization of Bi and Na cations during sintering
ceramic samples suggested their usefulness for energy storage
at high temperature [27–30]. Maximum induced strain
applications.
% values of ~0.62, 0.18, 0.15, 0.11and 0.09 were ob-
tained in x = 0, 0.04, 0.08, 0.12 and 0.16 ceramic
samples, respectively. Drastic decrease of induced
strain% with the increase of ST content in BNT-KNN-
ST system can be related to replacement of FE ordering
with AFE ordering [31].

Fig. 6 P-E hysteresis loops of the BNT-KNN-ST ceramic samples Fig. 8 S-E loops of the BNT-KNN-ST ceramic samples
 J Electroceram

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