Journal of Alloys and Compounds 829 (2020) 154573

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Enhancement of electrical energy storage ability by controlling grain

size of polycrystalline BaNb2O6 for high density capacitor application
D.K. Kushvaha a, B. Tiwari b, c, S.K. Rout a, *
a
Department of Physics, Birla Institute of Technology, Mesra, 835215, Ranchi, Jharkhand, India
b
Technical Physics Division, Bhabha Atomic Research Centre, Trombay, Mumbai, 400085, India
c
Homi Bhabha National Institute, Anushakati Nagar, Mumbai, 400094, India

a r t i c l e i n f o a b s t r a c t

Article history: The present article focuses on the electrical energy storage capacity of BaNb2O6 (BN) ceramic material with
Received 5 January 2020 varying sintering time duration of material synthesized by solid state reaction method. The crystal phase
Received in revised form formation during calcination process was studied with high temperature x-ray diffraction, which confirms
26 February 2020
the formation of desired crystalline phase at temperature above 1100
C. The associated micro-structural
Accepted 27 February 2020
Available online 29 February 2020
images reveal increasing trend of average grain size from 4.32 mm to 10.08 mm with raising sintering
time. A decrease in Z0 with temperature confirms the occurrence of negative temperature coefficient (NTCR)
behavior of BN ceramic similar to semiconductor material. The impedance spectroscopy provides the
Keywords:
Impedance spectroscopy
electrical equivalent circuit of investigated BN ceramic. Fitting of these data with three R and Q (CPE) el-
Energy storage ements connected in series revealed an important information regarding grain, grain boundary and elec-
Ferroelectric trode effects. The frequency dependent conductivity of the material follows the Jonscher’s power law and
found increase in frequency exponent n from 0.51 to 0.92 for BN05 to BN50 that suggests shifting of ionic
long-range translational motion to localized motion of ions/charge carriers. The activation energy, calcu-
lated from curve between relaxation time and inverse temperature, reduces from 0.59 eV to 0.33 eV for
sample BN05 to BN50. The recoverable energy increases from 2.12 to 10.28 mJ/cm3 with sintering time
interval whereas, the storage energy efficiency enhanced from 12.98% to 57.85%.
© 2020 Elsevier B.V. All rights reserved.

1. Introduction been widely investigated to meet the requirement of compact

With a growing concern of environmental protection, the health
hazard lead-based materials are required to substitute with suit-
able alternatives in the electronic world. So, an attempt is being
made to develop lead-free electrostatic high energy storage ca-
pacitors with high efficiency and recoverable energy.
The continuous development of electronic industry demands
high energy density dielectric material for application in different
field including pulse power circuits [1]. The prototype antiferro-
electric, relaxor ferroelectric and linear dielectric material has been
identified to be used for high energy devices but generally, the
antiferroelectric and relaxor ferroelectric materials are found to
possess higher energy density than linear dielectrics. The perov-
skite ceramic materials SrTiO3, BiTiO3(BT), BNKT, BNT, BiFeO3,
AgNbO3, Bi(Mg0.5Ti0.5)O3 (BMT), etc. and their solid solution has
* Corresponding author.
E-mail address: skrout@bitmesra.ac.in (S.K. Rout).
electronic and electrical devices [2e4]. N. Sun et al. optimized
(Bi0.5Na0.5)TiO3eBi(Ni0.5Zr0.5)O3 in form of thick film to achieve
ultrahigh recoverable energy 50.1 J/cm3 and corresponding effi-
ciency 63.9% underexposed electric field of 2200 kV/cm [5]. R.A.
Malik et al. reported the energy density̴ 1.0 J/cm3 with storage
efficiency 70% under the exposed field 60 kV/cm at temperature
range 25e135
C for ceramic 0.96Bi0.5Na0.84K0.16Ti0.97Nb0.03O3-
0.04SrTiO3 synthesized by traditional solid state reaction method
[6]. Another Bi-based ferroelectric material BiFeO3 (BF) has been
identified as an excellent candidate for energy storage devices due
to its greater intrinsic polarization (P > 100 mC/cm3) but at the same
time high current leakage restricts its application. But, the high
polarization of BiFeO3 has been paved the way for researchers to
investigate BF doped other perovskite material [7]. D. Zhen inves-
tigated relaxor ferroelectric material (0.67-x)BiFeO3eBaTiO3e
Ba(Mg1/3Nb2/3)O3 that reveals energy storage density 1.56 J/cm3
and storage efficiency 75% with applied field 125 kV/cm for x ¼ 0.06
composition [7].
The polycrystalline material of type AB2O6 series that

https://doi.org/10.1016/j.jallcom.2020.154573
0925-8388/© 2020 Elsevier B.V. All rights reserved.
2 D.K. Kushvaha et al. / Journal of Alloys and Compounds 829 (2020) 154573

encompasses SrNb2O6, SrxBa(1-x)Nb2O6, FeNb2O6, etc. is categorized Phase analyzer (SI 1260, Solartron, U.K.). The silver coated pellets
as tungsten bronze (TB) type. The material facilitates excellent were fired at temperature 500
C for 30 min before investigation in
technological application in the diverse field of electro-optics, py- order to remove the organic content in silver paste. The ferroelec-
roelectric and piezoelectric that ensure its position in laser tric loops were studied using a sophisticated ferroelectric loop
modulator, pyroelectric infrared detectors, ferroelectric devices, etc tracer (Precision Premier II, Radiant Tech, USA).
[8]. SrxBa(1-x)Nb2O6(SBN) is identified as a ferroelectric in previous
article for x < 0.60 while x > 0.60 represents relaxor behavior [9].
3. Result and discussion
The transparent SBN was also grown as a single crystal by the
Czochralski growth technique and observed spontaneous polari-
3.1. Structural and phase analysis
zation 0.65 C/m2 which is far better than other ferroelectric ma-
terials like Pb0.24Ba0.69Nb2O6, K3Li2Nb2O15, etc [8].
Fig. 1(a) depicts the x-ray diffraction pattern of BN calcined at
The present article reports a ferroelectric material BaNb2O6 (BN)
different temperatures (600e1150
C) along with stating and mixed
that lies in tungsten and bronze family. The article is among a few
precursors. The x-ray diffraction pattern has been engaged to un-
articles that reveal a non-perovskite structure for the application
derstand the phase formation mechanism of the material at
for high energy density storage devices. Within the article, an
different calcination temperatures. The figure depicts the domi-
attempt has been made to enhance storage energy density and
nancy of mixture phase of starting precursor BaCO3 and Nb2O6 up
corresponding efficiency with growing dense grain of the material.
to 900
C but peaks with asterisk “*” sign for material calcined at
The article also reflects the optimization of calcination temperature
900
C are a good agreement with PDF Card no. 00-014-0028 which
to synthesize BN in desired phase by solid state reaction method.
confirms the presence of an intermediate phase Ba5Nb4O15. The
The complementary electrical behavior of material has been
intermediate phase begins to react with precursor Nb2O5 with
investigated with the assistance with complex impedance spec-
increasing calcination temperature to form a final desired product
troscopy technique.
BN, which is confirmed with dominancy and suppression of x-ray
diffraction peak corresponding to BN and Ba5Nb4O15 phase
2. Experimental
respectively. Finally, all observed peaks for calcination temperature
range 1100e1150
C are in agreement with PDF card no. 01-074-
The lead-free tungsten and bronze type BN ceramic was fabri-
2201 without any secondary peak that suggests the orthorhombic
cated by the traditional solid-state reaction route. The high purity
phase with space group Pbmm. The proposed reaction mechanism
precursor BaCO3 (purity > 98%, Merck, Mumbai) and Nb2O5 (99.5%
involving in crystal phase formation of BN is given below
pure, Himedia, Mumbai) were used in stoichiometric ratio as a
starting material. The powder mixture was ground manually using
900o C
an agate mortar and pestle for 6 h in wet medium (acetone þ distill 5BaCO3 þ 2Nb2 O5







!Ba5 Nb4 O15 þ 5CO2
o (1)
water). The mixed powder was dried in IR lamp to get slurry, which 1100 1150 C
Ba5 Nb4 O15 þ 3Nb2 O5












!5BaNb2 O6
was calcined in closed alumina crucible within a programmable
furnace at different temperatures 600
C, 700
C, 800
C, 900
C, The observed result is an agreement with previous report by T.T
1000
C, 1100
C and 1150
C for 6 h to study the phase formation of Fang et al. [10]. The absence of any secondary phase for calcination
the material. The calcination process corresponding to each tem- temperature 1150
C indicates that each ion acquires the desired
perature was performed on a freshly mixed starting precursor. The position into the lattice. Fig. 2 shows the crystal structure of
formation of desired phase was confirmed by x-ray diffraction BaNb2O5 ceramics in the top and side views. The figure depicts the
pattern recorded by x-ray diffractometer (Smart Lab, Rigaku, Japan) top, bottom and middle plane perpendicular to the a-axis occupies
with Cu-Ka (1.54 Å) source. The desired calcined powder of BN at two Ba2þ atoms in each plane in diagonal. The Ba2þ ions occupying
temperature 1150
C was mixed with 5% polyvinyl alcohol (PVA) in the middle plane diagonal are in opposite diagonal relative to the
solution and uniaxially pressed in a 10 mm pellets with a hydraulic top and bottom plane. Between both extreme planes and the
press at pressure 100 kg/cm2. Thereafter, the resulting pellets were middle plane, there exist two planes that contain two Nb5þ ions in
sintered at temperature 1200
C for different duration 5 h, 20 h,
35 h and 50 h (abbreviated as BN05, BN20, BN35 and BN50
respectively). The morphological image of platinum polished pellet
was examined by scanning electron microscope (SEM, JSM-6390
LV, JEOL, Japan). The average grain size of samples BN05, BN20,
BN35 and BN50 was studied by the linear intercept method. The
Archimedes principle was employed to measure the bulk density
and apparent porosity of investigated samples using a hand-made
setup. The setup consists of a digital electronic balance, wired
sample holder with suspension arrangement, hot plate and a glass
beaker. The dry weigh of the pellets was measured by a digital
electronic balance and kept in a water beaker and heated. The pores
present in the pellets were completed filled with water, the weight
of pellets is recorded as shocked weight. After the shocked weight
is taken, the samples were suspended in water with the help of
wired hanger and the measured weight is recorded as suspended
weight. The experimental bulk density and apparent porosity were
measured by using the relation; bulk density ¼ dry weight/
(shocked weight-suspended weight) and the apparent porosity ¼
(shocked weight-dry weight)/(shocked weight-suspended weight).
The investigation of the electrical property was performed on silver
coated (Ted Pella) pellets with a sophisticated impedance/Gain- Fig. 1. x-ray diffractogram BN calcined at different temperature.
 D.K. Kushvaha et al. / Journal of Alloys and Compounds 829 (2020) 154573 3

the opposite diagonal. Neither any Nb5þ nor Ba2þ ion occupies the
corner and face of the orthorhombic unit cell.
The average crystallite size(D) of monophasic BN ceramic is
computed by the full-width half maxima (FWHM) for most intense
x-ray diffraction peak with the aid of Scherrer relation given by

Kl
D¼ (2)
b cos q

Where l ¼ 1.5405 Å is a wavelength of incident x-ray Cu Ka, b is full-

width half maxima (FWHM) and q is Bragg’s diffraction angle for
most intense diffraction peak. The estimated average crystallite size
for most intense peak is found to be 64.28 nm.

3.2. Scanning electron microscope

Fig. 3(aed) exhibits the micro-structural image of BN05, BN20,

Figure 2. Crystal structure of BaNb2O6.
BN35 and BN50 respectively at resolution x2500. The images reveal
the well-developed grain of material with irregular shape and size.
The development of some of grain in Fig. 3(d) is suppressed due to
the enlargement of neighboring grain. The images also reveal a clear
appearance of grain separation and the enhancement of grain size
with the increase in sintering time. The calculated average grain size

Fig. 3. (aed) Microstructure of BN05, BN20, BN35 and BN50 respectively, (e) average grain size of investigated samples and (f) experimental Bulk density and Apparent Porosity by
Archimedes Principle.
4 D.K. Kushvaha et al. / Journal of Alloys and Compounds 829 (2020) 154573
with the linear intercept method is shown in Fig. 3(e). The average
grain size increases significantly from 4.32 mm for BN05 to 10.08 mm
for BN50 because increasing sintering duration provides more
suitable time for grain growth mechanism. The enlargement of grain
size reduces the porosity of the material significantly which fulfills
the expectation to observe dense grain by increasing the sintering
time. The observation is a good agreement with the observed
experimental porosity shown in Fig. 3(f) by the Archimedes princi-
ple. The figure reveals a decrease in apparent porosity and an in-
crease in bulk density from BN05 to BN50 that raise the possibility to
be used the material as an energy storage device.
3.3. Impedance
Fig. 4(aed) exhibits the change in a real part of impedance Z0 as a
function of frequency (1 Hze1 MHz) at different temperatures
(400
Ce600
C at the step of 50
C) for BN05, BN20, BN35 and
BN50 respectively. The conventional trend of variation of Z0 with a
frequency for different temperatures has been observed. The fig-
ures describe the high and approximately constant impedance in
the low frequency range, while fall sharply to small value after
specific frequency which is associated with the release of space
charge [11]. The figure also reveals the significant decrease in Z0
with increasing temperature in smaller frequency region, whereas
merges for all temperatures after sharp fall of Z0 at higher frequency
region. The reduction of barrier height with gaining thermal energy
may be responsible for decreasing Z0 with raising the temperature
in lower frequency region. Thus, the material behavior is analogs to
Fig. 4. (aed) Variation of Z0 with frequency for BN05, BN20, BN35 and BN50 respectively, (e) Comparative Variation of Z0 with frequency for investigated samples at 500
C.
negative temperature coefficient resistance (NTCR) type, which is
similar to the behavior of other wideband semiconductors [12,13].
The Fig. 4(e) shows a comparative variation of Z0 for BN05, BN20,
BN35 and BN50 as a function of frequency at temperature 500
C.
The figure describes the increase of impedance from BN05 to BN50
toward a small frequency region while the curves merge with small
Z0 in higher frequency side. The increase in Z’ is associated with a
decrease in porosity and an increase in grain size with raising
sintering duration (depicted Fig. 3(eef)).
Fig. 5(aed) exhibits the variability in magnitude of the imaginary
part of impedance Z’’ with frequency at different temperatures
(within temperature range 400oCe600
C at the step of 50
C) for
investigated ceramic BN05, BN20, BN35 and BN50 respectively. The
observed peaks shift toward a higher frequency side and broaden
significantly with raising the temperature that indicates the tem-
perature dependent relaxation process of charge carrier [14]. Some
previous reports claim the broadening in peak represents the non
Debye behavior of material [15]. The figure also presents the evo-
lution of a new peak after exceeding a specific temperature at the
lower frequency side, which is attributed to the generation of more
ionic charges carrier with different relaxation time by gaining suf-
ficient thermal energy. Each observed peak in the figure corresponds
to the different relaxation time of carrier that is calculated with
uto ¼ 1, where u ¼ 2pf is the angular frequency and to represents
the most probable relaxation time. Fig. 5(e) displays the variation of
logarithmic of most probable relaxation time as a function of inverse
of temperature. The figure also displays the linear fit of experi-
mentally observed data with Arrhenius law up to an acceptable
 D.K. Kushvaha et al. / Journal of Alloys and Compounds 829 (2020) 154573
Fig. 5. (aed) Variation of Z’’ with frequency for BN05, BN20, BN35 and BN50 respectively, (e) variation of relaxation time with frequency and linear fit by Arrhenius law, (f)
Comparative Variation of Z’’ with frequency for investigated samples at 500
C.
value of goodness of fit. The most probable relaxation time is related
to activation energy(Ea) by following Arrhenius law [13]
Ea
to ¼ to ekB T
The calculated value of Ea form Arrhenius fit is plotted in Fig. 6 and
Fig. 6. Variation of activation energy for investigated samples.
5
shows a decrement in activation energy with increasing sintering
length, which may be associated with ease of ionic reorientation
due to reduction of potential barrier by the reduction of average
(3) grain surface area with increase in grain size (Fig. 3(e)). The
reduction in activation energy is a characteristic of fast charging
and discharging process of material, which is a requirement of
capacitors in pulse power circuit application. Moreover, Fig. 5(f)
shows the comparative variability of Z’’ for investigated samples at
a wide range of frequency 1Hz to 1 MHz at temperature 500
C. The
figure doesn’t show a significant change in the peak position but
the magnitude of Z” increases with raising temperature that sug-
gests decreased conductivity due to space charge of materials.
The complex impedance spectroscopy (CIS) is most acceptable
approach to examine the electrical behavior of low conduction
materials. The technique includes parameters like impedance,
admittance, dielectric permittivity, modulus are expressed in term
of complex quantity by following general formula [15]
j
Z * ¼ Z ’  jZ} ¼ R 
uCo
Y * ¼ Y ’ þ jY ’’ ¼ juCo ε*
(4)
ε* ¼ ε’  jε’’
1
M* ¼ ¼ M ’ þ jM ’’ ¼ juCo Z
ε*
Where, u ¼ 2pf ; Co ¼ εodA represents the angular frequency and
geometrical capacitance respectively. The influence of grain, grain
6 D.K. Kushvaha et al. / Journal of Alloys and Compounds 829 (2020) 154573

Fig. 7. (aed) Variation of Z0 with Z’’ for BN05, BN20, BN35 and BN50 respectively, (e) Comparative Variation of Z0 with Z’’ for investigated samples at 500
C, (f) Proposed electrical
equivalent circuit.

Table 1
Fitting parameters of complex impedance argand diagram for BN.

Rg(U) Rgb(U) Rel(U) ng ngb nel Qg Qgb Qel

BN05 2.482  104 9.780  103 7.534  103 0.7276 0.4849 0.7646 1.096  108 1.058  105 1.642  1010
BN20 6.652  104 1.782  104 1.104  104 0.7273 0.5867 0.8050 4.993  109 3.581  106 7.534  1010
BN35 7.533  104 3.157  104 1.341  104 0.7214 0.5058 0.8018 4.275  109 3.663  106 8.174  1010
BN50 1.133  106 3.744  105 227.1 0.6674 0.9436 0.3058 7.811  108 2.468  1011 7.127  106

boundary and interface effect in electrical properties of low con-
ducting polycrystalline material is generally investigated with the
application of CIS technique. Fig. 7(aed) exhibits an argand diagram
for complex impedance to investigate electrical behavior of poly-
crystalline BN05, BN20, BN35 and BN50 respectively for tempera-
ture range 400e600
C at the step of 50
C. Two semicircular arcs
(carrying information of grain, grain boundary and electrode effect)
with a depressed center below the real axis Z0 that attributes to the
departure from ideal Debye type of relaxation process of the ma-
terial can be observed in the figure (7). The lower end of Z0 corre-
sponds to high frequency Hf whereas the rightmost side of curve
represents low frequency Lf (indicated in the figure). The curvature
of arc is found to be temperature sensitive and decreases with the
elevation of temperature. The electrical information accommo-
dated in the semicircular arc is recovered through its fitting with an
electrical equivalent circuit in the electro-ceramic model. The
Fig. 7(e) shows a comparative argand diagram of complex imped-
ance along with its fitting for investigated BN05, BN20, BN35 and
BN50 at temperature 500
C. The fitting is performed up to an
acceptable level by a standard software Z-Simp win. The observed
semicircular arc fit well with the proposed electrical equivalent
circuit model containing three (RQ) elements connected in series,
 D.K. Kushvaha et al. / Journal of Alloys and Compounds 829 (2020) 154573
Fig. 8. (aed) Variation of ac conductivity with frequency for BN05, BN20, BN35 and BN50 respectively, (e) Comparative Variation of ac conductivity with frequency for investigated
samples at 500
C.
shown in Fig. 6(f). The symbol R and Q in the figure represent
resistance and constant phase element (CPE) whereas g, gb and el
in subscript indicate grain, grain boundary and electrode respec-
tively. The impedance of CPE is mathematically defined by the
following relation
1 region is referred as DC conductive region. Whereas, AC conduc-
ZQ ¼
ðjuÞn C
pffiffiffiffiffiffiffi
Where n is an empirical exponent, C is capacitance and j ¼ 1 is
an imaginary factor. Here, the empirical exponent factor is fitting
parameters with value lying between zero and unity, where n ¼ 0
and 1 represent for an ideal resistor and ideal capacitor respec-
tively. The fitting parameters are tabulated in Table 1. The table
reveals the elevation of resistance grain and grain boundary with
increases of sintering time, which may be predicted due to rela-
tively greater elongation of grain in the direction of movement of
mobile charge as compared to cross-section. Moreover, the curva-
ture of semicircular arc increases (shown in Fig. 6(e)) from BN05 to
BN50 that signifies the impedance enhancement which is an
agreement with experimental (Fig. 4(e)) as well as fitting param-
eter in Table 1.
3.4. AC conductivity
To explore the ionic dynamic of BN, frequency dependent con-
ductivity is investigated in a broad frequency range of 1 Hz to
7
1 MHz at various temperatures as well as different sintering time
length. The Fig. 8(aed) depicts the variability of AC conductivity as a
function of frequency for investigated BN05, BN20, BN35 and BN50
respectively. The figure represents a general trend in the variation
of AC conductivity with a response to the applied frequency. The
observed frequency independent conductivity in a lower frequency
(5)
tivity is strongly frequency dependent in higher frequency region,
which may be due to the disordering of cations in the neighboring
site [16]. The figure also reveals an increase in conductivity with an
increase in temperature that attributes to gain sufficient thermal
energy to activate the greater ions for participation in conductivity.
The appearance of double DC and AC conductive regions in higher
temperatures also suggests the inclusion of two independent
relaxation processes due to thermally activated ion [12]. The
presence of a double relaxation process in higher temperatures has
also been observed in Fig. 5(aed). The Fig. 8(e) represents a
comparative variability of AC conductivity with frequency for
investigated samples BN05, BN20, BN35 and BN50. The figure
shows that the conductivity decreases with raising sintering time,
which is attributed to the reduction of leakage current. The
observed decrease in conductivity may be a result of porosity
reduction depicted in Fig. 3(f) and enhancement of Z0 in Fig. 4(e).
Moreover, the Jonscher’s power law is the most acceptable tech-
nique by the researcher over the globe to analyze the ac conduc-
tivity of ceramic material, which is expressed by the following
relations [17]:
8 D.K. Kushvaha et al. / Journal of Alloys and Compounds 829 (2020) 154573

Table 2 motions.
Fitting parameters of Jonscher’s power law for BN in ac conductivity.

sac(x 104 Scm1) A(x 104) n R-Square

3.5. Ferroelectric and energy storage
BN05 3.728 3.728 0.5109 0.99939
BN20 2.745 2.580 0.6200 0.99962
The ferroelectric property of materials is influenced by micro-
BN35 2.580 2.745 0.6691 0.99917
BN50 0.304 0.304 0.9277 0.99689 structural properties, compositional modification and lattice defect
of the materials [18]. The Fig. 9(a) displays the room temperature P-
E hysteresis loop of BN05, BN20, BN35 and BN50 underexposed
field of 70 kV/cm2 and Fig. 9(b) display the variation of maximum
sðuÞ ¼ sdc þ Aun (6) polarization. The maximum polarization Pmax is observed to in-
crease significantly from Pmax ¼ 0.26 mC/cm2 to Pmax ¼ 0.51 mC/cm2
where sdc , n, A are DC conductivity (frequency independent), for BN05 to BN50 with (Pmax ¼ 0.45 mC/cm2). The significant in-
temperature dependent constant and frequency exponent respec- crease in Pmax is associated with ease of reorientation of ionic
tively. The frequency exponent n is a characteristic of the degree of dipole due to a decrease in activation energy (shown in Fig. 6).
interaction mobile ions with its surrounding environment. In other Moreover, the roundness in ferroelectric hysteresis loop may also
words, n decides the nature of mobile ionic motion from its state of be observed that increases from BN50 to BN05 and becomes very
potential energy minima to the neighboring minima [16]. The significant for BN05 that restricts to attain saturation polarization.
magnitude of n preceding unity represents the translational motion The roundness in ferroelectric hysteresis loop is attributed to the
of mobile ion, while motion becomes localized when exceeding conductive nature of material which is characteristic of porosity
unity. The fitting parameters of Jonscher’s power law in investi- and lattice defect of the material [19]. The figure also reveals a
gated BN ceramic at temperature a 500
C have been shown in significant gap between start and end point of measurement due to
Table 2. The tabulated value exhibits shifting of n (0.51e0.92) to- the presence of non-remnant components of material [20]. The
ward unity with increasing sintering time length for investigated recoverable energy Wrec and efficiency h can be calculated from the
samples that shows a decrement in the degree of ionic translational ferroelectric loop with a general equation is given by

Fig. 9. (a) P-E loop of BN at applied field 70 kV/cm, (b) Variation of maximum polarization with investigated BN.

Fig. 10. (a) Schematic diagram to calculate energy storage density and efficiency from PE hysteresis loop, (b) Recoverable energy and storage efficiency for investigated BN.
 D.K. Kushvaha et al. / Journal of Alloys and Compounds 829 (2020) 154573
Pðm
Wrec ¼ EdP
Pr
Wrec
h% ¼ X100
Wrec þ Wloss
Where, Wloss ,Pr and Pm are energy dissipate, remnant polarization
and maximum polarization respectively. The Fig. 10(a) shows the
schematic for calculation of energy -storage properties. The green
and yellow shaded area in the figure represents hysteresis energy
loss and recoverable energy storage density respectively. The
Fig. 10(b) exhibits the variation of recoverable energy and energy
storage efficiency (h%) for samples BN05, BN20, BN35 and BN50.
The figure shows a significant increase in Wrec (2.12e10.28 mJ/cm3)
and h% (12.98%e57.85%) with increasing sintering time 05 he50 h.
This significant increase may be associated with larger material
contributions as a result of an increase in density and reduction in
porosity as shown in Fig. 2 that reduces the leakage current. All the
sample were observed breakdown field higher than 120 kV/cm.
4. Conclusion
In summary, the phase formation study shows the successful
synthesis of BN ceramic at temperature above 1100
C by solid state
reaction route. The microstructural study shows a significant in-
crease in average grain size from 4.32 mm to 10.08 mm and reduction
of porosity with increase in bulk density by increasing sintering
time 05he50h that results. The examination of logarithmic relax-
ation time with inverse temperature reveals a remarkable decline
in activation energy from 0.59 eV to 0.33 eV for investigated sample
BN05 to BN50. The complex impedance spectroscopy study con-
firms non-Debye type of relaxation process of material and fits well
with an electrical equivalent circuit containing three parallel R and
Q elements connected in series. The variation of ac conductivity
with frequency obeys Jonscher’s power law and observed fre-
quency exponent n increases from 0.51 to 0.92 with increasing
sintering time 05 he50 h, which is associated with the transition of
long range ionic translational motion to localized motion. The Pmax
enhance significantly from Pmax ¼ 0.26 mC/cm2 to Pmax ¼ 0.51 mC/
cm2 with increasing sintering time length 5 he50 h, whereas Wrec
and h% increases 2.12e10.28 mJ/cm3 and 12.98%e57.85% respec-
tively. The breakdown field was found greater than 120 kV/cm.
Declaration of competing interest
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.
CRediT authorship contribution statement
D.K. Kushvaha: Writing - original draft. B. Tiwari: Supervision,
Writing - original draft. S.K. Rout: Supervision, Writing - original
draft.
Acknowledgements
One of the authors Mr. Dhiraj is thankful to Board of Research in
9
Nuclear Science (BRNS), Government of India, for providing finan-
cially support via project 34/14/11/2016-BRNS/34037.
(7)
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