Journal of
Materials Chemistry C
COMMUNICATION
Enhanced energy storage properties in sodium
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bismuth titanate-based ceramics for dielectric
Cite this: J. Mater. Chem. C, 2019,
7, 6222 capacitor applications†
Received 6th March 2019,
Accepted 23rd April 2019 Yichen Wu, ab Yuzhu Fan,ac Ningtao Liu, ac Ping Peng,ac Mingxing Zhou,
Shiguang Yan,a Fei Cao,a Xianlin Dong*acd and Genshui Wang*acd
DOI: 10.1039/c9tc01239g
rsc.li/materials-c
There are imperious demands for developing eco-benign energy
storage materials with high-performance in a sustainable society. In
this paper, we introduce Sr0.85Bi0.1&0.05TiO3 (SBT) and NaNbO3 (NN)
into Bi0.5Na0.5TiO3 (BNT) ceramics through compositional design.
The introduction of Sr2+ ions and vacancies at the A-sites constructs
relaxor ferroelectrics according to order–disorder theory. The
introduction of Nb5+ ions at the B-sites is confirmed to have two
major implications. In one way, it boosts a higher induced polarization
due to its intrinsic larger polarizability and overall stronger degree of
diffuseness. In another, it contributes to forming a core–shell micro-
structure, as proven using transmission electron microscopy, pro-
moting the breakdown strength (BDS) to a higher level. With the
above strategies, our BNT–SBT–4NN ceramics demonstrate excel-
lent energy storage performances with simultaneously ultrahigh
energy storage density (W B 3.78 J cm3), recoverable energy
storage density (Wrec B 3.08 J cm ) and efficiency (81.4%). Further-
3
more, the ceramics possess excellent discharge energy density
(Wd = 0.854 J cm3) and rapid discharge speed (t0.9 B 100 ns) in a
wide temperature range, proving their high application potential.
Our results break through the bottleneck of BNT-based ferroelectrics
with a general recoverable energy storage density of lower than
3 J cm3, making the BNT–SBT–4NN ceramic a powerful candidate
material for use in energy storage applications.
1. Introduction
To satisfy the demands for the rapid development of power
systems and electric devices, high power energy storage materials
a
Key Laboratory of Inorganic Functional Materials and Devices, Shanghai Institute
of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China.
E-mail: genshuiwang@mail.sic.ac.cn, xldong@mail.sic.ac.cn
b
Shanghai University, Shanghai 200444, China
c
University of Chinese Academy of Sciences, Beijing 100049, China
d
The State Key Lab of High Performance Ceramics and Superfine Microstructure
Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050,
China
† Electronic supplementary information (ESI) available. See DOI: 10.1039/c9tc01239g
6222 | J. Mater. Chem. C, 2019, 7, 6222--6230
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ac
have attracted extensive research attention.1–3 Among the numerous
energy-storage devices available (supercapacitors, batteries and
dielectric ceramics), dielectric ceramics exhibit competitive
performance in terms of high power density, excellent endurance
and fast charging–discharging capability, showing huge advan-
tages for use in weapons, vehicles and power electronics.4,5 Yet,
the relatively low energy storage density of dielectric ceramics
seriously limits their further potential applications.6,7 Thus,
exploring renewable energy storage materials with high energy
storage density is an urgent issue to tackle.8 Generally, the energy
storage of ceramics can be calculated by employing a polarization–
electric field (P–E) loop. The formulas are listed as follows:9–11
ð P max
Energy stroage density ðWÞ ¼ EdP (1)
0
ð P max
Recoverable energy stroage density ðWrec Þ ¼ EdP (2)
Pr
Wrec
Energy stroage efficiency ðZÞ ¼  100% (3)
W
where Pmax, Pr, P and E denote the maximum field-induced
polarization, remnant polarization, polarization and applied
electric field, respectively.12,13 The important factors for obtaining
a high energy density in dielectrics are a large Pmax, low Pr and
large breakdown strength,14 as shown in Fig. 1a. It is worth
noting that energy storage efficiency is also a crucial parameter
for practical application.15 In general, a low Z leads to significant
energy dissipation. Furthermore, lost energy will transform
into thermal energy and sharply decrease the breakdown electric
field. Hence, it is essential to develop energy storage materials
with outstanding energy storage density as well as high energy
efficiency.16
Relaxor ferroelectrics have been found to be promising
energy-storage materials owing to their large Pmax (induced)
and small Pr.17 Very recently, a large number of relaxor ferro-
electrics have been studied. For example, Shen et al.18 prepared
0.85BaTiO3–0.15BiYbO3 relaxor ceramics, which exhibit a Wrec
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Communication
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Fig. 1 (a) Schematic image showing energy storage properties under different electric fields. (b) Schematic image showing polar structure in relaxor
ferroelectrics under loading and unloading electric fields.
of 0.5 J cm3 with an Z of 93.1%, and Qiao et al.19 obtained the
0.93K0.5Na0.5NbO3–0.07Bi0.6(Mg1/3Nb2/3)O3 ceramics with a high
Wrec of 1.3 J cm3. However, the Pmax values of the ceramics
mentioned above are not large enough to enable a high Wrec,
which restricts their future applications.8 Bi0.5Na0.5TiO3 (BNT)-
based ceramics possess a large Pmax owing to their similar electron
configuration (lone 6s2 electron of Bi3+) to Pb2+ ions; unfortunately,
the large remanent polarization (Pr) of BNT ceramics seriously
hampers the achievement of high energy-storage properties. To
tackle this issue, many researchers achieved enhanced energy
storage properties in BNT-based relaxor ferroelectric films by
decreasing their Pr.20–22 Despite the great achievements made so
far, acquiring a large Wrec in bulk ceramics is still a tough
challenge.23,24
Here, we utilize the relaxor strategy to promote the energy
storage properties of BNT-based bulk ceramics. It is well known
that a charge and ion radius imbalance induces local random
fields in bulk ceramics, and that these local random fields
break the long-range ferroelectric order and generate a weak
short-range polar structure, which exhibits obvious relaxor
characteristics with a large Pmax and low Pr,14 as discussed as
follows. Usually, generated relaxor ferroelectrics with weakly
coupled short-range polar structures overcome the local barrier
easily and shift to being ferroelectric with long-range polar
structures under an electric field, exhibiting a large Pmax.
Meanwhile, when the electric field is removed, long-range polar
structures return to their origin state and exhibit a small Pr, as
shown in Fig. 1b. According to the above theory, we fabricated a
novel solution, 0.96(0.65Bi0.5Na0.5TiO3–0.35 Sr0.85Bi0.1&0.05TiO3)–
0.04NaNbO3 (abbreviated as 4NN), through a series of optimized
experiments and studied their energy storage properties. Sr2+ ions
and A-site vacancies in Sr0.85Bi0.1&0.05TiO3 (& represents the
vacancy) were introduced to the BNT perovskite structure to
break the position order, generating a weakly polar structure.
The addition of Nb5+ ions further modified its relaxor properties,
confirmed by a strong diffuseness degree. As a result, slim
pinched P–E loops were obtained, coupled with a high Pmax and
low Pr. In addition, a concentration gradient of Nb5+ ions formed
a core–shell structure, conducive to an excellent breakdown
strength (BDS) of B22 kV mm1 and a higher electric field
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induced Pmax in this novel bulk ceramic.25 Transmission electron
microscopy (TEM) was employed to demonstrate this peculiar
structure and uneven concentration distribution. With the above
strategies, 4NN solutions with a simultaneously ultrahigh recover-
able energy density (3.08 J cm3) and high efficiency (81.4%) were
acquired, breaking through the bottleneck of BNT-based ferro-
electrics with a general recoverable energy storage density of
lower than 3 J cm3.26
In addition, the charging–discharging performance is actually
vital to application, but only a few studies have focused on the
charging–discharging properties in BNT-based ceramics.27 In
order to evaluate the energy storage characteristics of the 4NN
ceramics, the overdamped charging–discharging properties
were investigated, where a high discharge energy density
(Wd = 0.854 J cm3) in a short time (t0.9 B 100 ns) was obtained,
superior to many other lead-free systems. The relaxor strategy
and experimental research results will hopefully serve as useful
feedback information for boosting energy storage properties in
BNT-based materials. These results lay the foundation for
energy storage applications utilizing BNT-based materials.
2. Experimental section
0.96(0.65Bi0.5Na0.5TiO3–0.35Sr0.85Bi0.1TiO3)–0.04NaNbO3 ceramics
were prepared using a conventional solid-state reaction technique.
Raw materials of Na2CO3 (99.99%), Bi2O3(99.99%), TiO2(99.98%),
Nb2O5(99.38%) and SrCO3(99.99%) were mixed with the addition
of alcohol according to a stoichiometric ratio. The mixed powders
were calcined at 850 1C after being ball-milled for 12 h. After that,
the powders were remixed again and pressed into disks with 6 wt%
polyvinyl alcohol (PVA) as the binder before sintering at 1160 1C.
Both circular surfaces of the ceramics were polished to a thickness
of 0.15–0.2 mm and were then coated with Au electrodes with a
diameter of 1.5 mm as electrodes.
X-ray diffraction (XRD) patterns of the as-prepared ceramics
at room temperature were recorded by using a diffractometer
(XRD, Bruker AXS, Karlsruhe, Germany) using Cu Ka (l = 1.5406 Å)
radiation. The microstructure of the as-sintered ceramics was
observed by using SEM (FE-SEM, S-4800, Hitachi, Tokyo, Japan).
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Fig. 2 (a) XRD patterns of the 4NN ceramics. (b) Bright field TEM image and selected area electron diffraction (SAED) patterns with the [110] zone axis of
the 4NN ceramics.
The temperature-dependent dielectric constant (er) and tangent
loss (tan d) were measured by using a broad dielectric Novocontrol
Alpha spectrometer (Nococontrol Technologies, Montabaur,
Germany) in the range of 50–300 1C. TEM characterization
was performed using a JEM-2100F electron microscope (JEOL,
Japan) with a double tilting stage, operating at 200 kV. The
polarization–electric hysteresis (P–E) loops was measured at
10 Hz, using a ferroelectric measurement system (aixACCT TF
Analyzer 2000, Aachen, Germany). The charge–discharge values
were obtained by using a specially designed RLC load circuit.
3. Results and discussion
Fig. 2a shows the XRD pattern of the 4NN ceramics at room
temperature. The pattern displays a single perovskite structure
without any impurities, indicating that Nb5+ and Sr2+ ions have
diffused into the lattice of the BNT ceramics. In this sample,
Nb5+ ions substituted for Ti4+ on the B-site while Sr2+ ions fill the
A-site in virtue of their similar ionic radii [Ti4+(0.604 Å, CN = 6),
Nb5+(0.64 Å, CN = 6), Bi3+(1.39 Å, CN = 12), Na+(1.39 Å, CN = 12),
Fig. 3 (a) SEM images of the 4NN ceramics. (b) Weibull distribution function of dielectric breakdown strength of the 4NN ceramics.
6224 | J. Mater. Chem. C, 2019, 7, 6222--6230
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and Sr2+(1.44 Å, CN = 12)]. The observed peak at around 2y = 311
is ascribed to the Kb X-rays contributions. From the inset
of Fig. 2a, the lack of splitting of both (111) and (200) diffraction
peaks indicates that the sample exhibits a pseudocubic phase.10,27,28
Furthermore, Selected Area Electron Diffraction (SAED) was utilized
to further ensure the phase structure of 4NN ceramics due to
the limited detection precision of XRD, as illustrated in Fig. 2b.
The weak super-lattice reflections of the 1/2(000) spots (marked
by an arrow) along the [110] zone axis imply the existence of a
ferroelectric R3c phase.29,30 The R3c polar phase inside the
pseudocubic phase is beneficial to induce high polarization
under an electric field.31
The microstructure of the 4NN ceramics was observed using
SEM, as shown in Fig. 3a. The sample displays a dense structure
with relatively few pores, the relative density of which is higher
than 96% measured through the Archimedes method. In order
to identify the average grain size of the ceramics, analytical
software (Nano Measure) was used to collect the grain size
distribution. As illustrated in the inset of Fig. 3a, the calculated
average grain size is about 1.48 mm, which is propitious to a high
breakdown strength (BDS). Fig. 3b exhibits the BDS of the 4NN
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Fig. 4 (a–c) HAADF images of the pure BNT, BNT–SBT and BNT–SBT–4NN ceramics; (d) bright-field TEM image of the 4NN ceramics; (e and f) EDS
analysis of the different ion distribution in the core–shell structure.

sample analyzed using the Weibull distribution, in which the
BDS can be obtained from the following equations:32,33
Xi = ln(Ei) (4)
   
i of Nb5+ ions may play a similar role in the BNT system. As is
Yi ¼ ln ln 1 1 (5)
1þn
where Ei denotes the breakdown strength of the samples
(E1 r E2 r. . .r En1 r En), i presents the number of each
sample (i = 1, 2. . .n1, n) and n is the total quantity of samples
(n = 10). The fitted values of BDS and b are 24.87 kV mm1 and
10.72, respectively. The high BDS value is ascribed to a dense
microstructure, less porosity, fine grain size and most importantly,
the core–shell structure, to be discussed as follows.
To further illuminate the microstructure, high-angle annular
dark field (HAADF) images were recorded of the pure BNT,
BNT–SBT and BNT–SBT–4NN ceramics, as shown in Fig. 4a–c.
Previous literature found that the uneven distribution of Nb5+ in
BaTiO3-based and Li2ZnTi3x(Al0.5Nb0.5)xO8 microwave ceramics
helped to form a core–shell structure,34,35 and the introduction
presented in Fig. 4a–c, one can see that the 4NN ceramics exhibit
a core–shell like structure with the size of about 150 nm, while a
similar structure could not be found in the pure BNT and BNT–
SBT ceramics. By using bright-field TEM, a twin boundary, which
is one of the characteristics of a core–shell structure, was also
obtained, as displayed in Fig. 4d. To further investigate the ion
distribution, energy-dispersive X-ray spectroscopy (EDS) was
employed by point scanning, through which nine points were
measured along a straight line passing through the core–shell
like structure, as shown in Fig. 4c. It was discovered that Nb5+
ions gather near the core/shell interface, displaying an obvious

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Fig. 5 (a) The dielectric permittivity and loss as a function of temperature, measured at different frequencies from 0.1 kHz to 1 MHz for the 4NN
ceramics. (b) Characterization of the diffuseness parameter g for the 4NN ceramics, Tm = 195 1C.

concentration gradient, while other ions disperse homogeneously
(Fig. 4e and f). According to the uneven distribution of Nb5+ ions
accompanied with the emergence of the twin boundary, it can
be safely concluded that the addition of Nb5+ ions is indeed
conducive to forming a core–shell structure, beneficial to boost-
ing a high BDS in 4NN ceramics, which is in agreement with
other perovskite systems.36,37
Fig. 5a shows the dielectric properties (dielectric constant er
and dielectric loss tan d) measured at different frequencies as a
function of temperature for the 4NN ceramics. Clearly, there
are two dielectric anomalies at Tm1 and Tm2, similar to other
BNT-based relaxor ferroelectrics. As frequency increases, er
decreases and the dielectric maximal temperature (Tm1 and
Tm2) shifts to a higher temperature, a feature typical of relaxor
ferroelectric ceramics. Besides, the broader dielectric constant
peaks also demonstrate the relaxor characteristic. To further
investigate the relaxor behavior, the degree of diffuseness (g)
1 1 ðT  T m Þg
was calculated by using the formula  ¼ , where
er em C (50.46 mC cm2) is obtained at 22 kV mm1, and the reason for
er is the dielectric constant corresponding to temperature T, em
stands for the maximum value of dielectric constant at Tm, and
C is the Curie constant.38,39 g varies between 1 (for a typical
ferroelectric) and 2 (for a complete relaxor ferroelectric).22 As
shown in Fig. 5b, the g value of the 4NN ceramics is extremely
close to 2, indicating powerful relaxor traits. The strong relaxor
behavior in this BNT–SBT–4NN ceramic mainly originates from
the improved local random electric/elastic fields caused by the
local compositional disorder.40 Moreover, the random fields
and local stresses due to the composition fluctuations would
weaken the long-range ferroelectric order and induce some
weakly coupled polar regions,14 changing the ferroelectrics into
relaxor ferroelectrics.
To illustrate the energy storage properties of this ceramic,
the room-temperature unipolar P–E loops of 4NN ceramics
measured at 10 Hz and under different electric fields are
presented in Fig. 6a. The samples display thin P–E loops with a
high Pmax and relatively low Pr, which are favorable for enhanced
Ð P max
energy storage. On account of the formula Wrec ¼ Pr EdP, the
maximum loading electric field Emax, Pmax and Pr are the crucial
factors to judge the energy-storage performance. Here, we
summarize these parameters in Fig. S1 (ESI†). It can be seen
that as the electric field increases, Pmax and DP (Pmax  Pr) rise
sharply with a slight increase of Pr, conducive to an enhanced
energy storage density. It is worth noting that the superior Pmax
this large polarization is discussed as follows. Profiting from the
larger polarizability of the Nb5+ ions replacing Ti4+ ions and the
remanent quasi-ferroelectric order helping the nucleation
growth of polar domains, a high induced polarization of polar
clusters is further promoted.41,42 Fig. 6b summarizes the electric
field dependent Wrec and Z values calculated using eqn (2) and
(3), in which Wrec ascends constantly while Z exhibits the reverse

Fig. 6 (a) P–E loops of 4NN ceramics with various compositions at 14 kV mm1 and 10 Hz. (b) The corresponding Wrec and Z values.

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Fig. 7 (a) Unipolar P–E loops of 4NN ceramics at different temperatures at a fixed frequency of 10 Hz, under an electric field of 16.5 kV mm1 and
(b) corresponding Wrec and Z values. (c) Room-temperature unipolar P–E loops of 4NN ceramics at different frequencies at 17.5 kV mm1 and
(d) corresponding Wrec and Z values.

tendency, attributed to the higher extrinsic contributions from
field-induced ferroelectric domain evolution. As a whole, by
means of compositional regulation and control, 4NN ceramics
break through the limitation that the Wrec of BNT-based relaxor
energy storage materials is generally less than 3 J cm3. These
results demonstrate that the BNT–SBT–4NN ceramic with
enhanced relaxor properties is a desirable material for advanced
energy storage devices.
Fig. 7a depicts the temperature-dependent unipolar P–E
loops for the 4NN samples measured in the temperature range
of 20 1C to 100 1C at 10 Hz and 16.5 kV mm1. As is illustrated, all
the loops display filament-like features with low hysteresis. When
the temperature increases from 20 1C to 100 1C, Pmax and Pr
slightly drop from 42.7 mC cm2 and 2.6 mC cm2 to 39.3 mC cm2
and 2.3 mC cm2, respectively (as exhibited in Fig. S2, ESI†).
Fig. 7b exhibits the Wrec and Z as a function of temperature.
Although there are some fluctuations in Wrec and Z during the
heating process, both Wrec and Z remain at more than 2.0 J cm3
and 80.0%, respectively. Fig. 7c presents the frequency dependence
of the unipolar P–E loops. Obviously, the 4NN sample displays
frequency insensitivity over the frequency range. With increasing
frequency, Pmax and Pr show no significant change (Fig. S3, ESI†),
and Wrec and Z slightly fluctuate from 2.5 J cm3 (1 Hz) to 2.3 J cm3
(100 Hz) and from 83.5% to 75.9%, respectively (Fig. 7d). These
results demonstrate that the Wrec and Z of 4NN ceramics possess
fine temperature and frequency stability.
Fig. 8a illustrates the electric-field dependent overdamped
pulsed discharge electric current–time (I–t) curves at room

Fig. 8 (a) Room-temperature overdamped pulsed discharge current curve of the 4NN ceramics as a function of electric field; (b) discharge energy
density of the 4NN ceramics under different electric fields; (c) the Wd and t0.9 values of the 4NN ceramics under different electric fields.

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Fig. 9 (a) Pulsed overdamped discharging current curves of the 4NN ceramics as a function of temperature; (b) discharge energy density of 4NN
ceramics at different temperatures.
temperature, in which the current reaches a peak quickly and
lasts r200 ns. The values of the current peaks depend on the
electric field, increasing from 3.6 A at 4 kV mm1 to 6.9 A at
10 kV mm1, as exhibited in the inset of Fig. 8a. The increase of
the current peak has a beneficial effect on the high discharge energy
Ð
density (Wd),43,44 according to the formula Wd ¼ R iðtÞ2 dt=V,
where R and V denote the total load resistance (285 O) and sample
volume, respectively.27 Fig. 8b depicts the calculated Wd–t curve
under various electric fields, among which t0.9 presented by the
dashed line describes the time needed to achieve 90% of the
maximum Wd value. The electric field dependent Wd and t0.9 values
are summarized in Fig. 8c, where Wd increases from 0.168 J cm3
to 0.854 J cm3 while t0.9 exhibits an opposite trend, reducing
from 120 ns to 103 ns when the electric field increases from
4 kV mm1 to 10 kV mm1 (inset of Fig. 8c). It is worth noting
that the Wd is slightly lower than the Wrec calculated using the P–E
loops, which is ascribed to the different measured frequency in
these two methods, as discussed as follows. It has been reported
that the domain walls are clamped by the viscous force Fv at high
frequency, thus the pulsed discharge equipment at a higher
working frequency blocks the contribution of the domain walls
to the energy storage density and results in a lower Wd value.
Fig. 10 Z versus Wrec value for the 4NN ceramic compared to other lead-
free systems.
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No matter what, all these results indicate that the 4NN ceramics
release a higher stored energy in a shorter duration under an
elevated electric field, exhibiting excellent charge–discharge
properties.
The temperature dependence of the overdamped discharge
properties was also investigated (Fig. 9a). The 4NN ceramics
exhibit similar overdamped discharge performance at different
temperatures, with the current peaks remaining steady in the
range of 20–160 1C, as presented in the inset of Fig. 9a. The
calculated temperature-dependent Wd–t curves are presented in
Fig. 9b. The Wd maintains a high value over a wide temperature
range, with a notable decrease of t0.9, as depicted in the inset of
Fig. 9b. The stability of the released stored energy corresponding
to a shorter duration at increasing temperature demonstrates
the high application potential for power systems.44
Fig. 10 exhibits the energy storage performance of the 4NN
samples compared with other lead-free systems.3–5,14,16,45–52
The BaTiO3-based system shows a high Z and low Wrec value
while the AgNbO3-based and (K0.5Na0.5)NbO3-based ceramics
exhibit the reverse tendency. BiFeO3-based and BNT-based
ceramics show similar energy storage performances, exhibiting
a medium Wrec (o2.0 J cm3). In this paper, the 4NN ceramics
possess a high Wrec value (3.08 J cm3) among BNT-based
ceramics and maintain a relatively high Z (81.4%), indicating
that BNT–SBT–4NN ceramics can be powerful candidate mate-
rials for use in energy storage applications.
4. Conclusion
An environment-friendly lead-free bulk ceramic, namely a BNT–
SBT–4NN ceramic, is designed in this paper. The introduction
of SBT and NN effectively breaks the ferroelectric long-range
order of the BNT ceramics and generates a weakly coupled
structure to form a relaxor phase. Enhanced relaxor properties
could be verified by the temperature-dielectric spectrum and
polarization-field hysteresis. The addition of NN not only
promotes the BDS of this BNT-based ceramic through a core–
shell structure, but also improves the saturated polarization
because of the larger polarizability of Nb5+ ions than Ti4+ ions.
Through compositional design, an ultrahigh recoverable energy
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storage density (3.08 J cm3) with excellent efficiency (81.4%) at
a high breakdown strength of 22 kV mm1 was obtained in the
BNT lead-free system, exhibiting outstanding performance of
energy storage properties. Furthermore, the 4NN ceramics possess
a relatively high discharge energy density (Wd = 0.854 J cm3) and
rapid discharge rate (t0.9 B 100 ns). These outstanding energy
storage values make the BNT–SBT–4NN ceramics an attractive
material in energy storage applications. Moreover, the design
strategy will hopefully serve as useful feedback information to
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boost energy storage properties in BNT-based materials.
Conflicts of interest
There are no conflicts of interest to declare.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (Grant No. 11774366) and International
Partnership Program of Chinese Academy of Sciences (Grant
No. GJHZ1821)
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