Ceramics International xxx (xxxx) xxx

Contents lists available at ScienceDirect

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

(Bi0.5Na0.5)TiO3-based relaxor ferroelectrics with simultaneous high energy

storage properties and remarkable charge-discharge performances under
low working electric fields for dielectric capacitor applications
Xinyu Zhao a, Chongyang Li a, Jikang Liu a, Yuqing Ding a, Wangfeng Bai a, *, Peng Zheng a, **,
Peng Li b, Jingji Zhang c, Jiwei Zhai d, ***
a
College of Materials and Environmental Engineering, Hangzhou Dianzi University, No. 2 Street, Hangzhou, China
b
College of Materials Science and Engineering, Liaocheng University, Liaocheng, 252059, China
c
College of Materials Science and Engineering, China Jiliang University, Hangzhou, 310018, China
d
Functional Materials Research Laboratory, School of Materials Science & Engineering, Tongji University, No. 4800 Caoan Highway, Shanghai, China

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

Keywords: High energy storage and charge-discharge performances under low electric field are desirable for lead-free
Relaxor ferroelectrics dielectric materials because of environmental hazards, the risk of high voltage and the high cost of insulation
Energy storage density technology. Herein, lead-free ceramics based on 0.6BNT-0.4Sr0.775Bi0.15TiO3 (BNT-SBT) were designed, which
(Bi0.5Na0.5)TiO3 lead-free ceramics
simultaneously achieves a large energy storage density (Wrec~ 2.41 J/cm3) and a high efficiency (η~87.5%)
Charge-discharge
Power density
under a low electric field of 190 kV/cm due to enhanced dielectric properties and the relaxation response.
Moreover, the energy storage properties of the BNT-SBT ceramic exhibit moderate temperature stability,
excellent frequency dependence, and cycling reliability. Furthermore, the charge-discharge performance
simultaneously features a high power density (PD~51.4 MW/cm3), an ultrafast discharge speed (t0.9–77 ns), and
remarkable stability against temperature and cycling. This study exploits a high-efficiency BNT-related ceramics
with concurrently high energy storage and charge-discharge performances under low electric fields, which
provides great potential in practical dielectric capacitor applications.

1. Introduction ∫Pm
Ws = Edp# (2)
Currently, to satisfy the increasing requirement for energy-storage 0

electronic devices, the employment of dielectric materials has received

considerable attention owing to their rapid charge-discharge capability, Wrec
η= × 100%# (3)
large power density, and excellent service life [1,2]. However, the low Ws
energy storage density (Wrec) and efficiency (դ) of dielectric capacitors
where Pmax, Pr and E represent the polarization maximum, remnant
remain obstacles, which significantly restrict potential applications.
polarization, and exerted electric field, respectively. As a result, to
Theoretically, Wrec and դ can be calculated from the polarization hys­
achieve superior energy storage performance (ESP), both a high (Pmax
teresis loop according to the basic formula given below [3]:
-Pr, ΔP) value and a large dielectric breakdown strength (Eb) are
∫Pm required in essence. In general, the Eb value can be enhanced by
Wrec = Edp# (1) modulating the fabrication process, sintering method, doping technol­
Pr ogy, structure design, and so on [4–6]. Pr can be readily tailored by
enhancing the dielectric relaxation characteristics, optimizing the phase

* Corresponding author.
** Corresponding author.
*** Corresponding author.
E-mail addresses: bwfcxj@126.com (W. Bai), zhengpeng@hdu.edu.cn (P. Zheng), apzhai@tongji.edu.cn (J. Zhai).

https://doi.org/10.1016/j.ceramint.2021.05.308
Received 9 May 2021; Received in revised form 27 May 2021; Accepted 30 May 2021
Available online 2 June 2021
0272-8842/© 2021 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Please cite this article as: Xinyu Zhao, Ceramics International, https://doi.org/10.1016/j.ceramint.2021.05.308
 X. Zhao et al. Ceramics International xxx (xxxx) xxx

Fig. 1. (a) XRD patterns, (b) SEM micrograph and average grain size, (c) element mapping images, and (d) atomic percentage of all elements for BNT-SBT ceramics.

structure, and introducing defect engineering [7–9]. In contrast, the Sr0.7Bi0.2TiO3 (SBT) into BNT is deemed as an excellent choice due to the
Pmax value is closely correlated with the gene of the material system, that desirable properties of a reduced Pr, maintenance of a large Pmax, and an
is, Pmax is mainly dominated by the element species [10,11]. Therefore, enhanced Eb [36]. To date, observably improved ESPs have been real­
the designed composition system with essentially high spontaneous ized using BNT-SBT-based RFE ceramics [13,15,37], yet there is little
polarization is crucial to achieve excellent ESP. information about BNT-SBT dielectric ceramics with high Wrec, high դ,
Among reported dielectrics, relaxor ferroelectrics (RFEs) have great good stabilities, and outstanding charge-discharge properties under a
advantages in high-energy storage applications, because of narrow low electric field. In particular, the charge-discharge performance will
hysteresis, high Pmax, small Pr and acceptable Eb, which afford remark­ directly reflect the real application capacity of dielectric materials,
able Wrec and դ values [12–14]. A number of RFEs based on environ­ which will definitively determine the use ability of energy storage de­
mentally friendly (Na0.5Bi0.5)TiO3 (BNT)-based materials have been vices [38]. Considering that Bi possesses the same lone-pair electronic
extensively explored, the Wrec values for which are usually located at 6s2 configuration as lead elements [5], from the structure-property
1–3 J/cm3 [15–17]. Recently, Qiao et al. realized a large Wrec of 3.62 relationship point of view, the Bi content has a significant impact on
J/cm3 with a դ of 89% at 246 kV/cm in 0.95 (0.6Bi0.5Na0.5 the ESP for dielectric ceramics. Under the guidance of the above­
TiO3-0.4Sr0.7Bi0.2TiO3)-0.05AgNbO3 (BNT-SBT-AN) ceramics [18–20]. mentioned thoughts, we selected a 0.6BNT-0.4(Sr1-1.5xBix)TiO3 relaxor
Yan et al. obtained 0.8BNT-0.2SrNb0.5Al0.5O3 (BNT-SNA) ceramics ceramic as a model to investigate the ESP. A large Wrec of 2.41J/cm3
fabricated by tape casting with an ultrahigh Wrec of 6.64 J/cm3 under a accompanied by a high η of 87.5% at low working electric field of 190
large field of 520 kV/cm [21]. Qi et al. achieved BNT-NaNbO3 (BNT-NN) kV/cm was achieved simultaneously in 0.6BNT-0.4(Sr0.775Bi0.15)TiO3
relaxor ceramics with record-high Wrec of 12.2J/cm3 and դ [22–24] of (BNT-SBT) ceramics, together with good stability against temperature,
69% at an ultrahigh field of 680 kV/cm [21]. However, the electric field frequency, and cycle numbers. More importantly, a large power density
driven high Wrec (>2 J/cm3) during charging and discharging is usually (PD~51.4 MW/cm3) and an ultrafast discharge rate (t0.9 = 77 ns) were
high (>200 kV/cm) for most RFEs, which places stricter requirements realized, revealing that the prepared ceramic is a significant candidate
on matching components and supporting insulation systems in practical with practical application potential under a low working electric field.
applications [25–29]. Thus far, some solutions to realize the low electric
field-driven high ESP have been reported by researchers, such as 2. Experimental section
introduction of effective end-members [15,18,30], adopting
hot-pressed/transient liquid-phase sintering approach [19,31], taking The 0.6BNT-0.4(Sr0.775Bi0.15)TiO3 (BNT-SBT) ceramics were fabri­
advantage of synergistic effect of multiple polar structures [32], and so cated by using a conventional solid-state reaction route. Reagent pow­
on. More crucially, increasing the field strength can generate an ders including Bi2O3, SrCO3, Na2CO3, TiO2, and BaCO3 (≥99%, all from
increased risk of dielectric breakdown, which inevitably leads to secu­ Aladdin) were applied as raw materials, which were weighed in light of
rity issues [33]. Additionally, low դ values signify more thermal energy the stoichiometric ratio. The dried oxide powders were ball milled in
and produce a temperature increase in the dielectric capacitors, thus absolute alcohol at 330 rpm for 8 h, calcined at 850 ◦ C for 2 h, and then
drastically leading to the failure of the capacitor and thermal stability in ball milled again to make the mixture more homogeneous. Afterwards, a
service [34]. Consequently, how to simultaneously tailor delightful Wrec, mixture of the obtained powders and 8 wt% PVA was formed and then
դ, and thermal stability under low electric field strength is a critical issue pressed into pellets with a thickness of 1 mm and a diameter of 10 mm.
in practical energy-storage capacitors [35]. After removing the PVA at 550 ◦ C for 10 h, the pressed disks were
To realize a high Wrec at a low electric field, the introduction of subjected to heat treatment at 1150 ◦ C for 2 h to obtain ceramic samples.

2
­
X. Zhao et al. Ceramics International xxx (xxxx) xxx

Fig. 2. Dielectric permittivity and loss as a function of (a) temperature and (b) frequency for BNT-SBT ceramics; (c) Comparison of dielectric temperature stability of
various dielectric ceramics; (d) The calculated diffuseness parameter γ, (e) dielectric constant, and (f) dielectric tunability with respect to bias electric field, (g) Z*
plots at different temperature and (h) Arrhenius plots for the indicated ceramics.

Finally, for energy storage performance measurement, the specimens microscopy (FE-SEM, S-4200, Hitachi, Tokyo, Japan). The P-E hysteresis
were ground and polished to a thickness of approximately 0.15 mm and loops were measured by a ferroelectric measurement system (RT1-Pre­
then sputtered with gold electrodes. mier II, Radiant Technologies InC, USA). The dielectric properties were
The phase structures were determined by X-ray diffraction (XRD; obtained by using an LCR meter (HP 4990 A; Agilent, Palo Alto, CA). An
MiniFlex 600, Rigaku, Japan). The microstructure and mappings of the ultraviolet spectrophotometer (TU-1901, Puxi Instruments Technology,
sintered ceramics were examined by field emission scanning electron China) was applied to obtain the band gap of the ceramics. The charge-

3
X. Zhao et al. Ceramics International xxx (xxxx) xxx

Fig. 3. (a) Unipolar P-E loops, (b) unipolar current curves, (c) the change of Pmax, Pr, Pmax-Pr, (d) Wrec and η with respect to electric field for BNT-SBT ceramics
measured at 10 Hz and room temperature, (e) the Weibull distribution of BDS, and (f) energy dependence of (αhν)2 on hν.

discharge performance was characterized by using a commercial system 150 ◦ C), exhibiting exceptional thermal stability. Apparently, the ce­
(CFD-003, Gogo Instruments Technology, China). ramics manifest a typical relaxor behavior, due to a strong dielectric
frequency dispersion [5]. To better estimate the degree of the diffuse­
3. Results and discussion ness, the value of the diffuseness parameter γ can be obtained from the
Curie-Weiss law: 1/εr - 1/εm = (T-Tm)γ/C, where Tm is the Curie tem­
Fig. 1(a) displays the XRD patterns for the BNT-SBT ceramic. The perature and C denotes the Curie-Weiss constant [15]. The plots of ln
ceramic samples possess a typical perovskite phase, demonstrating that (1/ε–1/εm) vs ln (T–Tm) are presented in Fig. 2(d). The γ value deter­
SBT is successfully dissolved into the BNT lattice. Moreover, a slight mined from the slope of the fitted line is 1.91, which indicates strong
trace of the Bi2Ti2O7 second phase is observed in the XRD patterns, relaxor ferroelectric character. The dependence of the dielectric con­
which can also be observed in SBT-based ceramics and may be ascribed stant and tanδ on frequency for the BNT-SBT ceramics is shown in Fig. 2
to excessive amounts of bismuth in the BNT-SBT system [39]. Consid­ (b). The dielectric constant displays a gradual reduction with increasing
ering the situation that the Bi2Ti2O7 shows no ferroelectricity and low frequency, and tanδ slightly increases to 0.13 at 1 MHz. The medium
dielectric constant (~115) [40], the existence of Bi2Ti2O7 second phase dielectric constant (1880 at 10 kHz) can guarantee a relatively high Pmax
may reduce the polarization and dielectric properties, thereby influ­ and the low loss can impede self-heating during the charge process,
encing the ESP. However, compared to the main phase, there is a very which is crucial to the enhancement of ESP. The substitution of Sr2+ and
slight trace of Bi2Ti2O7 secondary phase and thus the effect of Bi2Ti2O7 Bi3+ at the A-site produces a local charge imbalance, and, hence, an
phase on ESP can be neglected. Additionally, the inset in Fig. 1(a) shows improvement in the local random fields, yielding the frustration of the
amplified (110) and (200) diffraction peaks without splitting, indicating long-range ferroelectric order and flourishment of PNRs [5,15]. Fig. 2(c)
a pseudocubic phase structure in BNT-SBT ceramics. summarizes the recently reported temperature-related dielectric
The specimen exhibits a dense microstructure and homogeneous behavior of dielectric ceramics (BCTBNTNN [44], BMT-NBBT [45],
grain distribution, as displayed in Fig. 1(b). The average grain size for BNT-0.3BSN [46], BNT-BT-CZ [47], BNT-BT-NN [48], BT-BMN [49],
the sintered ceramic was determined to be ~1.06 μm (the inset of Fig. 1 BNT-BT-0.18KNN [50]), from which we can find that the designed ce­
(b)). In general, small grain size (G) is conductive to enhancing Eb for ramics maintain not only a large dielectric constant (>1800) but also a
dielectric ceramics as described by the relationship through Tunkasiri: relatively high upper operating temperature of 320 ◦ C, demonstrating
Eb ∝1/G− 1/2 [41]. In detail, the grain boundary fraction will increase as bright prospects in high-temperature capacitor applications.
the grain size decreases, which will lead to the increment of the deple­ The electric field-dependent dielectric constant for BNT-SBT
tion space charge layers building up at grain boundaries and thereby measured at different temperatures ranging from 25 ◦ C to 200 ◦ C is
produce high potential barriers for the charge carriers [11,42]. Fig. 1(c) displayed in Fig. 2(e). As the temperature increases, the dielectric con­
and (d) show the element mapping and atomic percentage for the stant first increases from 25 ◦ C to 60 ◦ C and then decreases from 60 ◦ C to
BNT-SBT ceramics. All elements are uniformly distributed in the 200 ◦ C, in accordance with the trend observed in the dielectric tem­
selected region. There is a certain disparity between the observed and perature spectra (Fig. 2(a)). To probe the dielectric stability against an
calculated atomic percentages because of the volatilization of Bi and Na electric field, the dielectric constant variation with the exerted electric
during sintering. A small grain size, dense microstructure and uniform field was evaluated by using the following formulation [51]: dielectric
element distribution favor the generation of a high Eb, thus enhancing constant variation (%) = εr (E)− εr (0)
εr (0) x100%, where εr (E) and εr (0) are the
the ESP [23,36,43]. dielectric constants at an applied bias electric field and zero field,
Fig. 2(a) depicts the dielectric properties of the BNT-SBT ceramics as respectively. As illustrated in Fig. 2(f), the dielectric constant variation
a function of temperature measured at different frequencies. The vari­ for the ceramics is less than 30% in the indicated temperature range
ation of the dielectric constant with temperature is less than ±15% from under a bias electric field of up to 60 kV/cm, displaying moderate sta­
40 ◦ C to 320 ◦ C, accompanied by a high dielectric constant of 1919 (at bility under an electric field attributed to the existence of ergodic relaxor

4
X. Zhao et al. Ceramics International xxx (xxxx) xxx

states.
To further study the influence of the electrical microstructure on
ESP, BNT-SBT ceramics were explored using impedance spectroscopy, as
manifested in Fig. 2(g). The ceramics have only a single semicircular
structure in the whole temperature range and electrical resistivity de­
creases increasing temperature. These observations indicate that the
grain response is crucial in the resistance and that oxygen vacancies in
grains are in the dominant positions at high temperature [23,52,53].
The activation energy Ea can be determined using the following equation
[15,37]:
( )
Ea
ω = ω0 ⋅exp # (4)
kB T

where ω0 is the pre-exponential constant, k denotes the Boltzmann

constant, and T presents the absolute temperature. Based on Arrhenius
plots of ln(R)-1000/T (Fig. 2(h)), the value of Ea for the ceramics was
determined to be 1.56 eV, suggesting extremely low oxygen vacancy
concentrations, and, thus, improved insulation for the ceramics [52]. In
summary, excellent dielectric characteristics, low oxygen vacancy con­
centrations, and good insulation responses can effectively boost Eb and
maintain a high Pmax, thus providing great potential in energy storage
applications.
The unipolar P-E loops as a function of electric field for BNT-SBT
ceramics are illustrated in Fig. 3 (a). It is worth noting that the ce­
ramics exhibit very narrow loops, which is indicative of typical relaxor
characteristics related to the dominant weakly polar phase. From the
corresponding electric field-current curves shown in Fig. 3(b), it is
observed that increasing the applied field produces increasingly obvious
peaks, further confirming the occurrence of field-induced local polari­
zation in PNRs and a high Pmax and small Pr at high driving fields [21,
54]. Fig. 3(c) displays the corresponding values for Pr, Pm, and ΔP. With
increasing electric field, Pmax gradually rises while Pr remains stable,
giving rise to an improvement in ΔP, which is an essential prerequisite
for evaluating the energy storage character. As shown in Fig. 3(d), the
Wrec values for the BNT-SBT ceramics increase monotonically from 0.81
J/cm3 to 2.41 J/cm3 with an increase in the external electric field from
80 kV/cm to 190 kV/cm. Interestingly, the BNT-SBT ceramic maintains
a stable η (>85%) in the whole electric field range and the η can still
maintain a high level of 87.5% at 190 kV/cm, implying low energy Fig. 4. Comparisons of (a) Wrec under different electric field and (b) Wrec and η
dissipation in terms of heat during the discharging process. between the BNT-SBT ceramics and other representative lead-free dielec­
For a pulse dielectric capacitor, Eb is an important parameter tric ceramics.
affecting ESP. Thus, the Weibull distribution function was adopted to
obtain the intrinsic Eb for the BNT-SBT ceramics, as presented in Fig. 3 so on) and external factors (sample area, sample thickness and electrode
(e). The exact Eb value can be obtained from the following equations shape/size, temperature, humidity, type of voltage, test duration, and so
[15,33,53]: on) [53]. Distinctly, the BNT-SBT ceramic possesses a wider Eg, which
Xi = ln(Ei )# (5) means it is difficult for electrons to jump from the valence band to the
conduction band, and, hence, a low possibility of intrinsic breakdown
⎛ ⎛ ⎞⎞
[11,14]. Moreover, as presented in Figs. 1(b) and Fig.2(c), the ceramics
⎜ ⎜
Yi = ln⎝ln⎝
1 ⎟⎟
# (6) also show relatively small grain size and moderate dielectric constant.
i ⎠⎠ As a result, the optimization of both extrinsic and intrinsic breakdown
1−
n+1 mechanisms guarantees high Eb, which provides a solid fundament for
superior ESP in BNT-SBT ceramics.
where Ei, i, and n represent the accurate value of Eb for each sample, the
To evaluate the ESP of BNT-SBT ceramics, comparisons of Wrec
sequence of the sample and the total quantity of the sample, respec­
values under different electric fields and Wrec/η found in the present
tively. Eb can be determined from the slope by linear fitting and the Eb
work and other representative lead-free dielectric ceramics (BNT-based
value reaches 241 kV/cm for the ceramics. To further verify the reason
[16,36,55,56]; BF-based [54,57,58]; BT-based [59]; NN-based [52];
for the improvement in Eb from an electronic structure viewpoint, the
KNN-based [60]; ST-based [39,61,62]) are summarized in Fig. 4(a) and
investigation of the band gap energy (Eg) from the UV–Vis absorption
(b), respectively. Notably, large Wrec values (>2J/cm3) generally
spectrum is presented in Fig. 3(f). The Eg can be acquired as follows [52]:
require high working electric fields (>200 kV/cm) for many reported
( )
(αhν)2 = A hν − Eg # (7) promising lead-free dielectric ceramics because of an insufficient Pmax
and large Pr. Although some BF-based ceramics exhibit high Wrec at low
The intersection between the tangent and the abscissa represents the fields, η is lower than 85% in recently reported literature. Encourag­
approximate Eg value, which is on the order of ~3.34 eV for BNT-SBT ingly, a high Wrec of 2.41J/cm3 along with an excellent η of 87.5% at low
ceramics. In general, the Eb value is governed by internal factors electric field (190 kV/cm) were realized concurrently in this study. This
(dielectric constant, Eg, density, defects, grain size, grain boundary, and achievement outperforms most previously reported lead-free dielectric

5
X. Zhao et al. Ceramics International xxx (xxxx) xxx

Fig. 5. Unipolar P-E loops [(a), (c), and (e)] and the variation of Wrec and η [(b), (d), and (f)] for BNT-SBT ceramics at different conditions: (a)–(b) temperature, (c)–
(d) frequency, and (e)–(f) cycle number.

ceramics, indicating that the designed ceramics hold broad prospects in kV/cm, showing a frequency-insensitive stability. These small changes
practical capacitor applications. in Pr and the hysteresis loss are basically connected with the time effect
To access the stability of the ESP of BNT-SBT ceramics, the influence of electric field induced long-range ferroelectric state returning to initial
of temperature, frequency, and cycle number on unipolar P-E loops was ergodic state or vice versa [57,58,64]. In comparison to a normal
measured and is presented in Fig. 5. Fig. 5(a) and (b) show the ferroelectric, the excellent frequency insensitivity of ESP for the
temperature-dependent unipolar P-E loops and ESP for BNT-SBT ce­ BNT-SBT sample was mainly ascribed to its highly-dynamic and smaller
ramics measured at 120 kV/cm and 10 Hz, respectively. The P-E hys­ size of PNRs due to large local random fields. Fatigue endurance is also
teresis increases substantially with increasing temperature, thus vital to ensure long-term charge and discharge stability for ceramic
generating an obvious decrease in the efficiency. This situation is capacitors. Therefore, the cycle number dependence of P-E loops and
thought to be linked with the facilitated hopping process of thermally ESP are tested, as demonstrated in Fig. 5(e) and (f). The P-E loops still
activated electrons or ions at elevated temperature [63]. Considering the hold a narrow shape after 105 cycles, and a small fluctuation in Wrec
decreased efficiency and nearly unchanged Pmax with increasing tem­ (<7%) is observed in the whole cycle number range. Therefore, the
perature, Wrec exhibits a certain reduction, characterized by an accept­ achieved ceramic exhibits outstanding fatigue endurance. The excellent
able variation of <17% (Fig. 5(b)). Fig. 5(c) depicts the P-E loops as a fatigue stability may be connected with the dense microstructure, low
function of frequency from 1 Hz to 500 Hz. The ceramics retain narrow oxygen vacancy concentration, and highly dynamic PNRs.
P-E loops in the whole frequency scope, revealing that the growth and The power density (PD), charge-discharge rate (t0.9), and discharge
orientation of PNRs relative to an external electric field mainly con­ energy density (Wd) are important performance indexes to directly es­
tributes to the polarization response process [63]. Fig. 5(d) shows that timate the practicability of dielectric capacitors. Fig. 6(a) and (b) depict
the Wrec value slightly fluctuates (<5% change), and the η values are not the underdamped discharge performance. It is evident that the first
lower than 80% over the whole frequency scope within 1–500 Hz at 120 current peaks are significantly boosted with increasing applied fields (E

6
X. Zhao et al. Ceramics International xxx (xxxx) xxx

Fig0. 6. Pulsed (a) underdamped and (c) overdamped discharge behavior for BNT-SBT ceramic at various electric fields (20–110 kV/cm); (b) Variations of Imax, CD,
and PD at different electric fields; (d) Wd as a function of time at various electric fields; (e) Comparison of the charge-discharge parameters of the ceramics with
recently reported lead-free ceramics.

= 20–110 kV/cm). From Fig. 6(b), the values for the current maximum As a result, a relatively large Wd of 0.51 J/cm3 at a low driving field of
(Imax), current density (CD = Imax/S), and power density (PD = E⋅Imax/2S; 110 kV/cm with an ultrafast discharge rate t0.9 = 77ns were simulta­
E: the exerted electric field, S: sample electrode area) increase dramat­ neously obtained. Note that, the energy density measured by the RC
ically increasing electric field, peaking at maximum values of Imax = circuit is lower than that measured in the P-E loop. The difference is
29.3 A, CD = 934 A/cm2, and PD = 51.4 MW/cm3 at 110 kV/cm, ascribed to the different time scales of the two measurements (P-E loop,
respectively. To obtain Wd, we measured the overdamped discharge 10− 1s; discharge measurement, 10− 5s) [63]. There is an equivalent se­
performance at different fields, as shown in Fig. 6(c). Meanwhile, the Wd ries resistor in the RC circuit measurement originated from various
versus time curves are also plotted in Fig. 6(d). Wd can be acquired from losses in the dielectric materials, thereby generating the loss of dis­
∫
R i(t)2 dt charged energy. To comprehensively estimate the advancement of this
the following formula [38]: Wd = , where R represents the load
V study, the charge-discharge performance in terms of Wd, t0.9, CD and PD
resistor (200Ω) in the circulating circuit, and V denotes the sample
for various recently reported lead-free energy storage ceramics [12,38,
volume. The t0.9 corresponds to the discharge time when 90% of the
43,52,56,65,66] was performed, as summarized in Fig. 6(e). Apparently,
stored energy has been released [65,66]. As the working field increases,
a high Wd, CD and PD together with ultrashort t0.9 at a low electric field
Wd and Imax increase linearly and the t0.9 fluctuates to a certain degree.
were obtained concurrently in this study, which precedes most lead-free

7
X. Zhao et al. Ceramics International xxx (xxxx) xxx

Fig. 7. The underdamped discharge waveforms and the change of Imax, CD, and PD as a function of [(a) and (b)] temperature and [(c) and (d)] cycle numbers for BNT-
SBT ceramics.

Fig. 8. [(a) and (c)] Overdamped discharge waveforms and [(b) and (d)] Wd versus time curves with respect to [(a) and (b)] temperature and [(c) and (d)] cycle
numbers for BNT-SBT ceramics, the insets show the change of t0.9 at different temperature and cycle number.

8
X. Zhao et al. Ceramics International xxx (xxxx) xxx

energy storage ceramics and is meaningful for practical pulse capacitor References
applications.
The temperature dependence of the underdamped discharge curves [1] Z. Yao, Z. Song, H. Hao, Z. Yu, M. Cao, S. Zhang, M.T. Lanagan, H. Liu,
Homogeneous/inhomogeneous-structured dielectrics and their energy-storage
are displayed in Fig. 7(a) under 70 kV/cm. Except for the nearly un­ performances, Adv. Mater. 29 (2017) 1601727.
varied first current peak, the positions of other peaks exhibit relative [2] Q. Li, F.-Z. Yao, Y. Liu, G. Zhang, H. Wang, Q. Wang, High-temperature dielectric
displacements with increasing temperature, mainly owing to certain materials for electrical energy storage, Annu. Rev. Mater. Sci. 48 (2018) 219–243.
[3] S. Wu, W. Li, M. Lin, Q. Burlingame, Q. Chen, A. Payzant, K. Xiao, Q.M. Zhang,
dielectric nonlinearity at various temperatures, as verified by Fig. 2(e) Aromatic polythiourea dielectrics with ultrahigh breakdown field strength, low
and (f). The Imax, CD, and PD with small changes present an ascending dielectric loss, and high electric energy density, Adv. Mater. 25 (2013) 1734–1738.
trend with increasing temperature (Fig. 7(b)), possibly because of the [4] F. Li, X. Hou, T. Li, R. Si, C. Wang, J. Zhai, Fine-grain induced outstanding energy
storage performance in novel Bi0.5K0.5TiO3-Ba(Mg1/3Nb2/3)O3 ceramics via a hot-
temperature-induced decrease in size and increased dynamics of PNRs pressing strategy, J. Mater. Chem. C 7 (2019) 12127–12138.
[67]. The excellent fatigue resistance of the charge-discharge property is [5] F. Li, M. Zhou, J. Zhai, B. Shen, H. Zeng, Novel barium titanate based ferroelectric
also essential for actual applications. Consequently, fatigue measure­ relaxor ceramics with superior charge-discharge performance, J. Eur. Ceram. Soc.
38 (2018) 4646–4652.
ments of the underdamped discharge curves were conducted, and the
[6] L. Zhao, Q. Liu, J. Gao, S. Zhang, J.F. Li, Lead-free antiferroelectric silver niobate
results are shown in Fig. 7(c) and (d). The CD and PD values are tantalate with high energy storage performance, Adv. Mater. 29 (2017) 1701824.
approximately 678A/cm2 and 24 MW/cm3, respectively, with a <9% [7] L. Fan, J. Chen, H. Kang, L. Liu, X. Xing, Structure, piezoelectric, and ferroelectric
change over the whole cycle number range, depicting excellent fatigue properties of BaZrO3 substituted Bi(Mg1/2Ti1/2)O3-PbTiO3 perovskite, J. Appl.
Phys. 111 (2012) 104118.
resistance performance, which favors the long-term use of ceramic ca­ [8] J. Wu, A. Mahajant, L. Riekehr, H. Zhang, Y. Bin, M. Nan, Z. Zhen, H. Yan,
pacitors in high-power systems. Perovskite Srx(Bi1-xNa0.97-xLi0.03)0.5TiO3 ceramics with polar nano regions for high
Fig. 8(a) and (b) evaluate the thermal stability of the overdamped power energy storage, Nanomater. Energy 50 (2018) 723–732.
[9] X. Ren, Large electric-field-induced strain in ferroelectric crystals by point-defect-
discharge behavior. Similar to other reported ceramics [67,68], there is mediated reversible domain switching, Nat. Mater. 3 (2004) 91–94.
a slight increasing tendency in Wd with increasing temperature, which is [10] E. Ronald Cohen, Origin of ferroelectricity in perovskite oxides, Nature 358 (1992)
ascribed to a more active dipole at high temperatures. The t0.9 with a 136–138.
[11] H. Qi, A. Xie, A. Tian, R. Zuo, Superior energy-storage capacitors with
small change exhibits a decreasing trend (inset of Fig. 8(b)), owing to the simultaneously giant energy density and efficiency using nanodomain engineered
accelerated polarization response rate arising from the decreasing size of BiFeO3-BaTiO3-NaNbO3 lead-free bulk ferroelectrics, Adv. Energy Mater. 10
PNRs [67,69,70]. Fig. 8(c) illustrates the overdamped discharge curves (2020) 1903338.
[12] Q. Hu, Y. Tian, Q. Zhu, J. Bian, L. Jin, H. Du, D.O. Alikin, V.Y. Shur, Y. Feng, Z. Xu,
as a function of cycle number. All curves maintain an almost unchanged X. Wei, Achieve ultrahigh energy storage performance in BaTiO3-Bi(Mg1/2Ti1/2)O3
current peak value of approximately 6.5 A after 5000 cycles. With the relaxor ferroelectric ceramics via nano-scale polarization mismatch and
cycle numbers increasing from 1 to 5000, Wd fluctuates in a small range reconstruction, Nanomater. Energy 67 (2020) 104264.
[13] F. Yan, K. Huang, T. Jiang, X. Zhou, Y. Shi, G. Ge, B. Shen, J. Zhai, Significantly
and the t0.9 remains steady around a very short time (~82 ns). The
enhanced energy storage density and efficiency of BNT-based perovskite ceramics
achieved thermal stability and fatigue endurance and the extremely via A-site defect engineering, Energy Stor. Mater. 30 (2020) 392–400.
short t0.9 are advantageous to a capacitor used at different operating [14] H. Qi, R. Zuo, A. Xie, A. Tian, J. Fu, Y. Zhang, S. Zhang, Ultrahigh energy-storage
conditions. density in NaNbO3-based lead-free relaxor antiferroelectric ceramics with
nanoscale domains, Adv. Funct. Mater. 29 (2019) 1903877.
[15] W. Ma, Y. Zhu, M.A. Marwat, P. Fan, B. Xie, D. Salamon, Z.-G. Ye, H. Zhang,
4. Conclusions Enhanced energy-storage performance with excellent stability under low electric
fields in BNT-ST relaxor ferroelectric ceramics, J. Mater. Chem. C 7 (2019)
281–288.
In summary, simultaneously high energy storage properties and [16] M. Yao, Y. Pu, H. Zheng, L. Zhang, M. Chen, Y. Cui, Improved energy storage
outstanding charge-discharge performance were realized in BNT-SBT density in 0.475BNT-0.525BCTZ with MgO addition, Ceram. Int. 42 (2016)
8974–8979.
ceramics via the enhancement of the dielectric properties and relaxa­
[17] L. Zhang, Y. Pu, M. Chen, T. Wei, W. Keipper, R. Shi, X. Guo, R. Li, X. Peng, High
tion response. As a result, a large Wrec of 2.41 J/cm3 and a high η of energy-storage density under low electric fields and improved optical transparency
87.5% under a low working electric field of 190 kV/cm, together with in novel sodium bismuth titanate-based lead-free ceramics, J. Eur. Ceram. Soc. 40
(2020) 71–77.
medium thermal stability, excellent frequency dependence, and fatigue
[18] X. Qiao, D. Wu, F. Zhang, B. Chen, X. Ren, P. Liang, H. Du, X. Chao, Z. Yang,
life, were achieved in the indicated ceramics, which breaks through the Bi0.5Na0.5TiO3-based relaxor ferroelectric ceramic with large energy density and
dilemma that a high Wrec value (>2 J/cm3) usually requires a high high efficiency under a moderate electric field, J. Mater. Chem. C 7 (2019)
applied electric field (>200 kV/cm) for most BNT-related dielectric 10514–10520.
[19] P. Gao, Z. Liu, N. Zhang, H. Wu, A.A. Bokov, W. Ren, Z.-G. Ye, New
ceramics. Moreover, the BNT-SBT ceramics also possess a high PD of antiferroelectric perovskite system with ultrahigh energy-storage performance at
51.4 MW/cm3, an ultrafast t0.9 of 77 ns, and excellent thermal stability low electric field, Chem. Mater. 31 (2019) 979–990.
and fatigue endurance, which is significant for energy-storage electronic [20] X. Qiao, F. Zhang, D. Wu, B. Chen, X. Zhao, Z. Peng, X. Ren, P. Liang, X. Chao,
Z. Yang, Superior comprehensive energy storage properties in Bi0.5Na0.5TiO3-based
devices in actual operating environments. This work demonstrates that relaxor ferroelectric ceramics, Chem. Eng. J. 388 (2020) 124158.
BNT-based ceramics possess dual characteristics with a high Wrec and [21] F. Yan, X. Zhou, X. He, H. Bai, J. Zhai, Superior energy storage properties and
great PD at low electric fields, enabling BNT-SBT ceramics to be a excellent stability achieved in environment-friendly ferroelectrics via composition
design strategy, Nanomater. Energy 75 (2020) 105012.
promising competitive material for practical applications in pulse-power [22] K. Bi, M. Bi, Y. Hao, W. Luo, Z. Cai, X. Wang, Y. Huang, Ultrafine core-shell
devices. BaTiO3@SiO2 structures for nanocomposite capacitors with high energy density,
Nanomater. Energy 51 (2018) 513–523.
[23] M. Zhou, R. Liang, Z. Zhou, X. Dong, Achieving ultrahigh energy storage density
and energy efficiency simultaneously in sodium niobate-based lead-free dielectric
Declaration of competing interest
capacitors via microstructure modulation, Inorg. Chem. Front. 6 (2019)
2148–2157.
The authors declare that they have no known competing financial [24] M.-X. Zhou, R.-H. Liang, Z.-Y. Dong, Novel BaTiO3-based lead-free ceramic
interests or personal relationships that could have appeared to influence capacitors featuring high energy storage density, high power density, and excellent
stability, J. Mater. Chem. C 6 (2018) 8528–8537.
the work reported in this paper. [25] Y. Tian, L. Jin, H. Zhang, Z. Xu, X. Wei, E. Politova, S.Y. Stefanovich, N.
V. Tarakina, I. Abrahams, H. Yan, High energy density in silver niobate ceramics,
J. Mater. Chem. 4 (2016) 17279–17287.
Acknowledgements [26] L. Zhang, Y. Pu, M. Chen, Influence of BaZrO3 additive on the energy-storage
properties of 0.775Na0.5Bi0.5TiO3-0.225BaSnO3 relaxor ferroelectrics, J. Alloys
The authors would like to acknowledge the Natural Science Foun­ Compd. 775 (2019) 342–347.
[27] M. Zhou, R. Liang, Z. Zhou, S. Yan, X. Dong, Novel sodium niobate-based lead-free
dation of Zhejiang Province (LY20E020008, LQ16E020004), and the
ceramics as new environment-friendly energy storage materials with high energy
National Natural Science Foundation of China (Grant No. 51802063, density, high power density, and excellent stability, ACS Sustain. Chem. Eng. 6
51502067). (2018) 12755–12765.

9
X. Zhao et al. Ceramics International xxx (xxxx) xxx

[28] M. Spreitzer, M. Valant, D. Suvorov, Sodium deficiency in Na0.5Bi0.5TiO3, J. Mater. [51] C. Zhu, Z. Cai, B. Luo, L. Guo, L. Li, X. Wang, High temperature lead-free BNT-
Chem. 17 (2007) 185–192. based ceramics with stable energy storage and dielectric properties, J. Mater.
[29] F. Gao, X. Dong, C. Mao, W. Liu, H. Zhang, L. Yang, F. Cao, G. Wang, Energy- Chem. 8 (2020) 683–692.
storage properties of 0.89Bi0.5Na0.5TiO3-0.06BaTiO3-0.05K0.5Na0.5NbO3 lead-free [52] C. Sun, X. Chen, J. Shi, F. Pang, H. Zhou, Simultaneously with large energy density
anti-ferroelectric ceramics, J. Am. Ceram. Soc. 94 (2011) 4382–4386. and high efficiency achieved in NaNbO3-based relaxor ferroelectric ceramics,
[30] Q. Yang, M. Zhu, Q. Wei, M. Zhang, M. Zheng, Y. Hou, Excellent energy storage J. Eur. Ceram. Soc. 41 (2021) 1891–1903.
performance of K0.5Bi0.5TiO3-based ferroelectric ceramics under low electric field, [53] G. Wang, J. Li, X. Zhang, Z. Fan, F. Yang, A. Feteira, D. Zhou, D.-C. Sinclair, T. Ma,
Chem. Eng. J. 414 (2021) 128769. X. Tan, D. Wang, I.M. Reaney, Ultrahigh energy storage density lead-free
[31] J. Yin, Y. Zhang, X. Lv, J. Wu, Ultrahigh energy-storage potential under low electric multilayers by controlled electrical homogeneity, Energy Environ. Sci. 12 (2019)
field in bismuth sodium titanate-based perovskite ferroelectrics, J. Mater. Chem. 6 582–588.
(2018) 9823–9832. [54] N. Liu, R. Liang, Z. Zhou, X. Dong, Designing lead-free bismuth ferrite-based
[32] N. Sun, Y. Li, X. Liu, X. Hao, High energy-storage density under low electric field in ceramics learning from relaxor ferroelectric behavior for simultaneous high energy
lead-free relaxor ferroelectric film based on synergistic effect of multiple polar density and efficiency under low electric field, J. Mater. Chem. C 6 (2018)
structures, J. Power Sources 448 (2020) 227457. 10211–10217.
[33] Z. Fan, Y. Yu, J. Huang, Q. Zhang, Y. Lu, Y. He, Excellent energy storage properties [55] W. Bai, L. Wang, X. Zhao, P. Zheng, F. Wen, L. Li, J. Zhai, Z. Ji, Tailoring frequency-
over a wide temperature range under low driving electric fields in NBT-BSN lead- insensitive large field-induced strain and energy storage properties in (Ba0.85Ca0.15)
free relaxor ferroelectric ceramics, Ceram. Int. 47 (2021) 4715–4721. (Zr0.1Ti0.9)O3-modified (Bi0.5Na0.5)TiO3 lead-free ceramics, Dalton Trans. 48
[34] P. Zhao, H. Wang, L. Wu, L. Chen, Z. Cai, L. Li, X. Wang, High-performance relaxor (2019) 10160–10173.
ferroelectric materials for energy storage applications, Adv. Energy. Mater. 9 [56] X. Zhao, W. Bai, Y. Ding, L. Wang, S. Wu, P. Zheng, P. Li, J. Zhai, Tailoring high
(2019) 1803048. energy density with superior stability under low electric field in novel (Bi0.5Na0.5)
[35] Q. Yuan, F.Z. Yao, S.D. Cheng, L. Wang, Y. Wang, S.B. Mi, Q. Wang, X. Wang, TiO3-based relaxor ferroelectric ceramics, J. Eur. Ceram. Soc. 40 (2020)
H. Wang, Bioinspired hierarchically structured all-inorganic nanocomposites with 4475–4486.
significantly improved capacitive performance, Adv. Funct. Mater. 30 (2020) [57] D. Zheng, R. Zuo, Enhanced energy storage properties in La(Mg1/2Ti1/2)O3-
2000191. modified BiFeO3-BaTiO3 lead-free relaxor ferroelectric ceramics within a wide
[36] A. Chen, Y. Zhi, High, purely electrostrictive strain in lead-free dielectrics, Adv. temperature range, J. Eur. Ceram. Soc. 37 (2017) 413–418.
Mater. 18 (2006) 103–106. [58] D. Zheng, R. Zuo, D. Zhang, L. Yang, Novel BiFeO3-BaTiO3-Ba(Mg1/3Nb2/3)O3 lead-
[37] Z. Pan, D. Hu, Y. Zhang, J. Liu, B. Shen, J. Zhai, Achieving high discharge energy free relaxor ferroelectric ceramics for energy-storage capacitors, J. Am. Ceram.
density and efficiency with NBT-based ceramics for application in capacitors, Soc. 98 (2015) 2692–2695.
J. Mater. Chem. C 7 (2019) 4072–4078. [59] H. Sun, X. Wang, Q. Sun, X. Zhang, Z. Ma, M. Guo, B. Sun, X. Zhu, Q. Liu, X. Lou,
[38] D. Li, Y. Lin, Q. Yuan, M. Zhang, L. Ma, H. Yang, A novel lead-free Na0.5Bi0.5TiO3- Large energy storage density in BiFeO3-BaTiO3-AgNbO3 lead-free relaxor ceramics,
based ceramic with superior comprehensive energy storage and discharge J. Eur. Ceram. Soc. 40 (2020) 2929–2935.
properties for dielectric capacitor applications, J. Materiomics. 6 (2020) 743–750. [60] B. Chen, Y. Tian, J. Lu, D. Wu, X. Qiao, P. Liang, H. Du, Z. Peng, X. Ren, X. Chao,
[39] X. Kong, L. Yang, Z. Cheng, S. Zhang, Bi-modified SrTiO3-based ceramics for high- Z. Yang, Ultrahigh storage density achieved with (1-x)KNN-xBZN ceramics, J. Eur.
temperature energy storage applications, J. Am. Ceram. Soc. 103 (2019) Ceram. Soc. 40 (2020) 2936–2944.
1722–1731. [61] P. Zhao, B. Tang, F. Si, C. Yang, H. Li, S. Zhang, Novel Ca doped Sr0.7Bi0.2TiO3 lead-
[40] J. Roberto Esquivel-Elizondo, B. Hinojosa, J. Nino, Bi2Ti2O7: it is not what you free relaxor ferroelectrics with high energy density and efficiency, J. Eur. Ceram.
have read, Chem. Mater. 23 (2011) 4965–4974. Soc. 40 (2020) 1938–1946.
[41] T. Tunkasiri, G. Rujijanagul, Dielectric strength of fine grained barium titanate [62] P. Zhao, B. Tang, Z. Fang, F. Si, C. Yang, G. Liu, S. Zhang, Structure, dielectric and
ceramics, J. Mater. Sci. Lett. 15 (1996) 1767–1769. relaxor properties of Sr0.7Bi0.2TiO3-K0.5Bi0.5TiO3 lead-free ceramics for energy
[42] R. Waser, The role of grain boundaries in conduction and breakdown of perovskite- storage applications, J. Materiomics. 7 (2021) 195–207.
type titanates, Ferroelectrics 133 (1992) 109–114. [63] J. Li, F. Li, Z. Xu, S. Zhang, Multilayer lead-free ceramic capacitors with ultrahigh
[43] W.-B. Li, D. Zhou, L.-X. Pang, R. Xu, H.-H. Guo, Novel barium titanate based energy density and efficiency, Adv. Mater. 30 (2018) 1802155.
capacitors with high energy density and fast discharge performance, J. Mater. [64] E. Sapper, N. Novak, W. Jo, T. Granzow, J. Rödel, Electric-field-temperature phase
Chem. 5 (2017) 19607–19612. diagram of the ferroelectric relaxor system (1-x)Bi1/2Na1/2TiO3-xBaTiO3 doped
[44] A. Zeb, Y. Bai, T. Button, S.J. Milne, W. Jo, Temperature-stable relative with manganese, J. Appl. Phys. 115 (2014) 194104.
permittivity from -70◦ C to 500◦ C in (Ba0.8Ca0.2)TiO3-Bi(Mg0.5Ti0.5)O3-NaNbO3 [65] G. Liu, Y. Li, B. Guo, M. Tang, Q. Li, J. Dong, L. Yu, K. Yu, Y. Yan, D. Wang,
ceramics, J. Am. Ceram. Soc. 97 (2014) 2479–2483. L. Zhang, H. Zhang, Z. He, L. Jin, Ultrahigh dielectric breakdown strength and
[45] P. Chen, B. Chu, Improvement of dielectric and energy storage properties in Bi excellent energy storage performance in lead-free barium titanate-based relaxor
(Mg1/2Ti1/2)O3-modified (Na1/2Bi1/2) 0.92Ba0.08TiO3 ceramics, J. Eur. Ceram. Soc. ferroelectric ceramics via a combined strategy of composition modification, viscous
36 (2016) 81–88. polymer processing, and liquid-phase sintering, Chem. Eng. J. 398 (2020) 125625.
[46] L. Zhang, X. Pu, M. Chen, S. Bai, Y. Pu, Influence of BaSnO3 additive on the energy [66] W. Liu, J. Gao, Y. Zhao, S. Li, Significant enhancement of energy storage properties
storage properties of Na0.5Bi0.5TiO3-based relaxor ferroelectrics, J. Eur. Ceram. of BaTiO3-based ceramics by hybrid-doping, J. Alloys Compd. 843 (2020) 155938.
Soc. 38 (2018) 2304–2311. [67] P. Zhao, B. Tang, Z. Fang, F. Si, C. Yang, S. Zhang, Improved dielectric breakdown
[47] M. Acosta, J. Zang, W. Jo, J. Rödel, High-temperature dielectrics in CaZrO3- strength and energy storage properties in Er2O3 modified Sr0.35Bi0.35K0.25TiO3,
modified Bi1/2Na1/2TiO3-based lead-free ceramics, J. Eur. Ceram. Soc. 32 (2012) Chem. Eng. J. 403 (2021) 126290.
4327–4334. [68] G. Liu, M. Tang, X. Hou, B. Guo, L. Jin, Energy storage properties of bismuth ferrite
[48] W. Jia, Y. Hou, M. Zheng, M. Zhu, High-temperature dielectrics based on (1-x) based ternary relaxor ferroelectric ceramics through a viscous polymer process,
(0.94Bi0.5Na0.5TiO3-0.06BaTiO3)-xNaNbO3 system, J. Alloys Compd. 724 (2017) Chem. Eng. J. 412 (2020) 127555.
306–315. [69] J. Li, Z. Shen, X. Chen, S. Yang, W. Zhou, M. Wang, L. Wang, Q. Kou, Y. Liu, Q. Li,
[49] T. Wang, L. Jin, C. Li, Q. Hu, X. Wei, D. Lupascu, Relaxor ferroelectric BaTiO3-Bi Z. Xu, Y. Chang, S. Zhang, F. Li, Grain-orientation-engineered multilayer ceramic
(Mg2/3Nb1/3)O3 ceramics for energy storage application, J. Am. Ceram. Soc. 98 capacitors for energy storage applications, Nat. Mater. 19 (2020) 999–1005.
(2015) 559–566. [70] X. Liu, R. Rao, J. Shi, J. He, Y. Zhao, J. Liu, H. Du, Effect of oxygen vacancy and A-
[50] J. Zang, W. Jo, H. Zhang, J. Rödel, Bi1/2Na1/2TiO3-BaTiO3 based thick-film site-deficiency on the dielectric performance of BNT-BT-BST relaxors, J. Alloys
capacitors for high-temperature applications, J. Eur. Ceram. Soc. 34 (2014) 37–43. Compd. 875 (2021), 159999.

10