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High-performance lead-free bulk ceramics for

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Cite this: DOI: 10.1039/d1ta04504k

electrical energy storage applications: design
strategies and challenges
Zetian Yang,a Hongliang Du, *b Li Jin *c and Dirk Poelman *a

Received 27th May 2021
Accepted 20th July 2021
DOI: 10.1039/d1ta04504k
rsc.li/materials-a
Compared with fuel cells and electrochemical capacitors, dielectric capacitors are regarded as promising
devices to store electrical energy for pulsed power systems due to their fast charge/discharge rates and
ultrahigh power density. Dielectric materials are core components of dielectric capacitors and directly
determine their performance. Over the past decade, extensive efforts have been devoted to develop
high-performance dielectric materials for electrical energy storage applications and great progress has
been achieved. Here, we present an overview on the current state-of-the-art lead-free bulk ceramics for
electrical energy storage applications, including SrTiO3, CaTiO3, BaTiO3, (Bi0.5Na0.5)TiO3, (K0.5Na0.5)NbO3,
BiFeO3, AgNbO3 and NaNbO3-based ceramics. This review starts with a brief introduction of the
research background, the development history and the basic fundamentals of dielectric materials for
energy storage applications as well as the universal strategies to optimize their energy storage
performance. Emphases are placed on the design strategies for each type of dielectric ceramic based on
their special physical properties with a summary of their respective advantages and disadvantages.

a
LumiLab, Department of Solid State Sciences, Ghent University, Krijgslaan 281-S1,
9000 Gent, Belgium. E-mail: dirk.poelman@ugent.be
b
College of Engineering, Xi'an International University, Xi'an 710077, China. E-mail:
duhongliang@126.com; duhongliang@mail.xjtu.edu.cn
c
Electronic Materials Research Laboratory, Key Laboratory of the Ministry of
Education, International Center for Dielectric Research, School of Electronic
Science and Engineering, Xi'an Jiaotong University, Xi'an 710049, China. E-mail:
ljin@mail.xjtu.edu.cn

Zetian Yang is a Ph.D. student in Hongliang Du is currently a full

LumiLab, Department of Solid
State Sciences, Ghent University.
His research interests mainly
include piezoresistive properties
of samarium monosulde, inor-
ganic photochromic materials
for optical information storage
and anti-counterfeiting applica-
tions, and ferroelectric ceramics
for electrical energy storage. He
has authored/co-authored 17
referred papers with three highly
cited papers and one hot paper, and his work has been cited about
1000 times.
professor at college of Engi-
neering, Xi'an International
University (XAIU), China. He
received his Ph.D. degree from
Northwestern Polytechnical
University in 2011, and he was
a visiting scholar in Technische
Universitat Darmstadt (Ger-
many) in 2016. His research
interests mainly include lead-
free piezoelectric materials,
high-temperature piezoelectric
ceramics, transparent ferroelectric ceramics and dielectric mate-
rials for energy storage applications. He received several awards
including Natural Science Second Class Award from Ministry of
Education (2010), Excellent Paper Award for Young Scientists from
the 11th IUMRS International Conference in Asia (2010), and the
First Prize of Scientic and Technological Award from Shaanxi
Universities (2021). He has published more than 80 papers in the
eld of ferro/piezoelectric materials. He was identied as one of
the top 1% of highly cited authors in Royal Society of Chemistry
(RSC) journals in 2019.

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Journal of Materials Chemistry A
Challenges along with future prospects are presented at the end of this review. This review will not only
accelerate the exploration of higher performance lead-free dielectric materials, but also provides
a deeper understanding of the relationship among chemical composition, physical properties and energy
storage performance.
1. Introduction
As the conict between the shortage of fossil fuels and the
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increased energy demand intensies, efficient storage and
utilization of energy are becoming more and more important.
For electrical energy storage, fuel cells, batteries, super-
capacitors and dielectric capacitors are regarded as four
promising devices.1–3 Comparatively, dielectric capacitors can
achieve an ultrahigh power density (
107 W kg1) owing to their
fast charge/discharge rates (<100 ns) because they store and
release electrical energy through dielectric polarization and
depolarization upon external electrical elds instead of chem-
ical reaction.4–8 Beneting from the ultrahigh power density,
dielectric capacitors allow various promising applications such
as hybrid electric vehicles, pacemakers and electronic circuits,
as shown in Fig. 1a. However, the energy storage density of
dielectric capacitors is relatively low (102 to 101 W h kg1) in
comparison with fuel cells and batteries, which cannot meet the
requirements of miniaturization and lightweight of electronic
components and hence limits their wide applications. Conse-
quently, if the energy storage density of dielectric capacitors
could be enhanced to be comparable to that of electrochemical
capacitors or even lithium batteries, more extensive applica-
tions of dielectric capacitors would become possible.
A dielectric capacitor consists of a dielectric material
between two electrodes, as shown in Fig. 1b–e. Without the
dielectric material, the capacitance (C0) of the capacitor can be
Li Jin is a full professor in the
School of Electronic Science and
Engineering at Xi'an Jiaotong
University (XJTU), China. He
received his BEng and MEng
degrees in Electronics Science
and Technology from the XJTU
in 2003 and 2006, respectively.
He received his PhD degree in
Materials Science and Engi-
neering from the Swiss Federal
Institute of Technology in Lau-
sanne (EPFL), Switzerland in
2011. Subsequently, he completed his postdoctoral research at the
Ceramics Laboratory of EPFL. His interests include ferroelectric/
electrostrictive/dielectric materials and their applications in
actuators, energy storage devices and other electronic devices. He
has published more than 110+ papers in peer-reviewed journals
with 6000+ citations. One of his paper has been selected as the 100
Most Inuential International Academic Papers in China, in 2014.
He has received the First Prize of Natural Science Award by the
Ministry of Education of China (2015).
J. Mater. Chem. A
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expressed by the equation C0 ¼ (30A)/d, where 30 is the vacuum
permittivity, A is the area of the metal plates and d is the
distance between the two plates, as displayed in Fig. 1b. Aer
charging, the amount of charge stored on the plates can be
calculated by the equation Q0 ¼ C0V, where Q0 and V represent
the stored charge and the applied voltage value, respectively.
When a dielectric material is inserted between the two plates,
the particles bound by chemical bonds in the dielectric are
initially in a random direction before applying an external
electric eld, as shown in Fig. 1c. Upon applying an external
electric eld, the positive and negative charge centers of the
particles will be separated and then move a nite displacement
in the direction of the electric eld or the opposite direction of
the electric eld to form electric dipoles, as presented in Fig. 1d.
Aer polarization, bound charges are generated at the surface of
the dielectric. These charges will generate a depolarizing elec-
tric eld inside the dielectric, which in turn causes the power to
supply more electric charge to the plates to maintain the
potential difference between the plates. Aer inserting
a dielectric material with a dielectric constant of 3r between the
two plates, the capacitance of the capacitor is enhanced to C (C
¼ C0 + C1 ¼ 303rA/d), and the charge stored in the capacitor is
increased from Q0 to Q (Q ¼ Q0 + Q1), as displayed in Fig. 1d. The
stored energy can be released when connecting to an external
load. However, a small part of the stored energy cannot be
released (Q2 in Fig. 1e) because of the existence of the remnant
polarization of the dielectric material. Aer charging, the
Dirk Poelman is a full professor
in the Department of Solid State
Sciences at Ghent University,
Belgium since 2012. He ob-
tained his PhD in Ghent
University on electroluminescent
thin lms in 1994. His recent
interests include photocatalysis
for air purication, luminescent
materials for lighting and
displays, persistent luminescent
compounds for safety applica-
tions and near-infrared bio-
imaging. He has published over 230 international publications
in these elds. Currently, he is working on the relation between the
persistent luminescent behaviour of materials, their thermolumi-
nescence characteristics and their photo- and thermochromic
properties.
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Fig. 1 (a) The promising applications of dielectric capacitors. Principle of dielectric capacitors for electrical energy storage: (b) dielectric
capacitors without dielectric materials after charging; dielectric capacitors with dielectric materials (c) before charging, (d) after charging and (e)
after discharging.
energy that can be released in per unit volume is called the
recoverable energy storage density (Wrec), and the efficiency (h)
is dened as the ratio of released electrical energy to stored
electrical energy during a charging/discharging process. In
short, the energy stored in the capacitor comes from the power
source and is stored in the electric eld inside the dielectric
material. The energy storage capacity of the capacitor can be
increased by 3r/30 times under the same applied electric eld
aer inserting the dielectric. Consequently, dielectric materials
are regarded as the core component of dielectric capacitors and
directly determine their performance. In the past two hundred
years, dielectric material has gone from water to oil, to glass, to
mica and to current ceramics, polymers and composites.9
Correspondingly, the capacitor has evolved from the original
Leiden bottles and mica capacitors to the present solid state
capacitors.10,11 Currently, there are mainly four kinds of dielec-
tric materials for capacitors, namely, polymer, ceramic, glass-
ceramic and ceramic-polymer composites.12–19 Generally, poly-
mer exhibits a high dielectric breakdown strength (Eb > 1000
kV cm1) but a low 3r (3r z 10), resulting in a relatively low Wrec
(Wrec < 2 J cm3), even for the widely used biaxially orientated
polypropylene-based capacitors.20–22 Also, the performance of
polymer capacitors deteriorates signicantly under a high
working temperature (>120  C), which hinders their applica-
tions in extreme conditions such as deep-well drilling and
aircras.23–25 To improve their performance, ceramics with
a high 3r have been incorporated into polymers to develop
ceramic-polymer composites.26–28 Although the energy storage
performance can be enhanced, this kind of dielectric material is
faced with issues of the aggregation of ceramics llers and the
interface incompatibility between ceramics and polymers. For
glass-ceramics, these materials simultaneously exhibit the
advantages of the high Eb of glasses and the large 3r of ferro-
electrics, but the interface effect between the amorphous phase
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and crystalline phase has a negative effect on the energy storage
performance.29,30 Meanwhile, the preparation of high-quality
glass-ceramics with pore-free microstructure is also a chal-
lenging task.31,32 In contrast with polymers, ceramics possess
a high 3r, a moderate Eb and good thermal stability, and are
therefore regarded as promising candidates for dielectric
capacitors, especially for high-temperature applications.
However, the Wrec of dielectric ceramics is relatively low because
of their low Eb, which needs to be further improved. Fig. 2a
shows the statistical data on related publications from 2010 to
2020, based on a search in “ISI Web of Science” by using the
keywords of “dielectric” and “energy storage”. The number of
publications related to this subject continuously increases and
exceeds 700 per year in 2019. To better understand this situa-
tion, we collected the statistics on the percentage of publica-
tions in 2010–2020 for different types of dielectric materials. As
shown in Fig. 2b, dielectric ceramics received the most atten-
tion among the four types of dielectric materials. Meanwhile, in
the global capacitor market, ceramic capacitors command more
than half of the market. The global market of ceramic capaci-
tors has continued to increase in the past ten years and is pre-
dicted to reach 24 billion dollars in 2025, and ceramic
capacitors have become an indispensable basic component in
industrial production.33 Moreover, lead-free materials are
preferred for consumer electronics over lead-based materials
due to environmental regulations.34,35 Consequently, the
research on lead-free dielectric ceramics for capacitors has
attracted more research interest (see Fig. 2a), and has become
one of the most active academic research areas in advanced
functional materials in the past decade.
According to their thickness, dielectric ceramics for elec-
trical energy storage can be divided into three categories: thin
lms (<1 mm), thick lms (1–100 mm) and bulk ceramics (>100
mm). Generally, thin lms usually exhibit a high Eb because of
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the lower amount of defects and impurities, leading to a high
Wrec. Up to now, the highest Wrec was achieved in SrTiO3 thin
lms with a value of 307 J cm3 for lms grown on a La0.67-
Sr0.33MnO3 electrode.36 However, the total energy stored in the
thin lms is relatively low due to their small volume, hindering
their widespread applications. Compared with thin lms, thick
lms can be fabricated into a multilayer structure to store more
electrical energy while maintaining a relatively high Eb. In
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good energy storage properties, their thin or thick lms usually
have a better energy storage performance. For example, the Wrec
of 0.90BaTiO3-0.10Bi(Mg2/3Ti1/3)O3 ceramic in its bulk form and
thin lm is 1.13 J cm3 and 32.5 J cm3, respectively.37,38 The
Wrec of 0.55(Na0.5Bi0.5)TiO3-0.45(Sr0.7Bi0.2)TiO3 ceramics in bulk
form and multilayer capacitors (MLCC) is 2.5 J cm3 and 9.5 J
cm3, respectively.39 In other words, the research on bulk
materials can provide preliminary exploration for the develop-

addition, the relatively small volume and high Eb of thick lms
make them more conducive to device integration than bulk
ceramics. Bulk ceramics exhibit the advantages of easy fabri-
cation, low cost, superior mechanical properties, and the large
volume endows them with the ability to store more electrical
energy. Also, if the bulk form of dielectric materials possesses
ment of high-performance thin and thick lms, and hence bulk
materials are attracting more and more research interest
because of their low cost and facile preparation process in
comparison with thick and thin lms. This conclusion is also
conrmed by the statistical results of the publications on
dielectric materials in the form of ceramics, thin lms, thick

Fig. 2 (a) The statistical data on publications from 2010 to 2020 by searching the keywords of “dielectric” and “energy storage” in “ISI Web of
Science”. (b) Publications on different types of materials for energy storage in ceramic, polymer, glass-ceramic and composite, and (c) publi-
cations on dielectric materials for energy storage with the form of ceramic, thin film, thick film and MLCC in refereed journals in the time period of
2010–2020. (d) The development history of lead-free bulk ceramics for energy storage (BT-BS: 0.7BaTiO3-0.3BiScO3, KNN-ST: 0.85(K0.5Na0.5)
NbO3-0.15SrTiO3, BNT-NN: 0.78(Bi0.5Na0.5)TiO3-0.22NaNbO3, NN-BNT: 0.76NaNbO3-0.24(Bi0.5Na0.5)TiO3).

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Table 1 Reviews related to dielectric materials for energy storage in the past 10 years

Title of article Journals Year Contents Ref.

Novel ferroelectric polymers for Macromolecules 2012 Strategies to improve the 70

high energy density and low loss polarization of polymers
dielectrics
A review on the dielectric J. Adv. Dielect. 2013 Progress of several kinds of 53
materials for high energy-storage dielectric materials
application
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Homogeneous/inhomogeneous- Adv. Mater. 2017 Status and perspectives of 58

structured dielectrics and their different types of dielectrics and
energy-storage performances their composites
High-temperature dielectric Annu. Rev. Mater. Res. 2018 Summarize the progress and 21
materials for electrical energy challenges of dielectric materials
storage for high-temperature applications
High-performance dielectric Adv. Funct. Mater. 2018 Some effective approaches to 57
ceramic lms for energy storage improve the performance of
capacitors: progress and outlook ceramic-based lms
Antiferroelectrics for energy Adv. Mater. Technol. 2018 Preparation, characterization and 56
storage applications: a review optimization of antiferroelectric
ceramics
High-energy-density ferroelectric Mater. Today 2019 Current status on the 64
polymer nanocomposites for microstructure design and
capacitive energy storage: material performance of PVDF-
enhanced breakdown strength based composites
and improved discharge efficiency
Glass-ceramic dielectric materials J. Mater. Chem. C 2019 Status and perspectives of glass- 66
with high energy density and ceramics for energy storage
ultra-fast discharge speed for high
power energy storage applications
Interface design for high energy Chem. Soc. Rev. 2019 Overview of the interface design 68
density polymer nanocomposites and structures of polymer based
composites
Perovskite lead-free dielectrics for Prog. Mater. Sci. 2019 Analyze the underlying 48
energy storage applications mechanisms and the research
progress of different dielectric
materials
Multiscale structural engineering Nanoscale 2020 Focus on the relationship between 49
of dielectric ceramics for energy the multiscale structures and
storage applications: from bulk to energy storage properties
thin lms
Lead-free antiferroelectric J. Mater. Chem. A 2020 Discuss the progress of AgNbO3 60
niobates AgNbO3 and NaNbO3 for and NaNbO3-based AFE bulk
energy storage applications ceramics
Review on the development of J. Mater. Chem. C 2020 Summarize the advance of some 59
lead-free ferroelectric energy- nonlinear ceramics and their
storage ceramics and multilayer composites
capacitors

lms and MLCC. As Fig. 2c shows, the research on bulk
ceramics comprises
64% of the total share. Currently, the
actively studied lead-free bulk ceramics include SrTiO3 (ST),
CaTiO3 (CT), BaTiO3 (BT), (K0.5Na0.5)NbO3 (KNN), BiFeO3 (BF),
(Bi0.5Na0.5)TiO3 (BNT), AgNbO3 (AN) and NaNbO3 (NN)-based
ceramics. These ceramics can be divided into linear materials
(ST and CT) and nonlinear materials (BT, KNN, BF, BNT, AN and
NN) based on their dielectric response characteristics. Fig. 2d
summarizes the development history of lead-free bulk ceramics
for electrical energy storage. The research on this subject can be
traced back to the 1990s, and it has become a research hotspot
since 2014.40 Here, we review the development of new material
systems and the improvement of Wrec. As Fig. 2d shows, the
initially studied material is ST, but its Wrec is relatively low (
1 J
cm3) in spite of a long period of research. One of the landmark
events was that Ogihara et al. reported the energy storage
performance of 0.7BT-0.3BiScO3 ceramics and obtained a Wrec
of 2.3 J cm3 with a thickness of 0.2 mm in 2009.41 Aerwards,
although researchers have successively developed new material
systems including BNT, CT and BF-based ceramics in 2011,
2012 and 2014, respectively, the Wrec was not greatly improved
and remains at around 2 J cm3.42,43 However, in 2016, Yang
et al. developed KNN-based ceramics for electrical energy
storage and achieved a Wrec of 4.03 J cm3 in 0.85KNN-0.15ST.44
Since then, the Wrec of lead-free bulk ceramics begins to enter
the range above 4 J cm3. Subsequently, Zhao et al. also

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Journal of Materials Chemistry A
obtained a Wrec of 4.2 J cm3 in AN-based anti-ferroelectric
(AFE) ceramics.45 Aer that, the Wrec of lead-free bulk
ceramics has been improved rapidly together with the devel-
opment of new material systems. Through the unremitting
efforts of researchers, the Wrec of lead-free bulk ceramics has
been enhanced from the original
1 J cm3 to the current 12.2 J
cm3, and the Wrec of corresponding MLCC has reached 21.5 J
cm3.46,47 In addition, the types of materials have evolved from
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the initial relaxor ferroelectric (RFE) materials to later AFE
materials and then to the present development of relaxor-
antiferroelectric (RAFE) materials. The regulation scale has
evolved from device conguration to sample microstructure
and then to the domain structure. However, the Wrec of most
reported lead-free bulk ceramics is still below 4 J cm3 and the
failure to simultaneously achieve a high Wrec and a high effi-
ciency (h) still needs to be solved. Apart from Wrec and h,
thermal stability, fatigue properties and mechanical perfor-
mance are also important characteristics for capacitors working
in severe conditions, such as high mechanical pressure, high
temperature and high vibration. In general, although great
achievement has been realized in the past decade, lead-free
bulk ceramics with high energy-storage performance are still
highly expected to speed up their wide applications.
In the past ten years, the progress of dielectric materials for
energy storage has been reviewed from a variety of perspectives
and in different stages, which have greatly promoted the
research progresses and result in some of the major break-
throughs.21,48–66 These reviews and their main contents are listed
in Table 1. For example, Zhu et al. introduced orientational
polarization in polar polymers for achieving high energy density
Fig. 3 Outline of this review.
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and low dielectric loss.67 Yao et al. concentrated on the advances
in glass-based and polymer-based inhomogeneous dielectrics.58
Li et al. described the progress and challenges of polymers,
polymer nanocomposites, and their thin lms for high-
temperature applications.21 Luo et al. discussed the interface
design and structure of polymer-based composites for energy
storage.68 Yang et al. stressed the underlying mechanisms of
dielectric breakdown and polarization for energy storage.48 Yao
et al. provided a survey on the multiscale engineering of
dielectric materials to optimize the energy storage perfor-
mance.49 More recently, Zhang et al. summarized the advances
of some nonlinear ceramics and their composites.59 However,
most of these reviews emphasized the advances of glass, poly-
mer and composites and their thin or thick lms for energy
storage applications. There is no special review related to the
design strategies to explore high-performance dielectrics based
on their unique physical properties. Especially in the “Research
Fronts 2020”, issued by the Institutes of Science and Develop-
ment under the Chinese Academy of Sciences, National Science
Library and Clarivate Analytics, the research on “lead-free
ceramics for energy storage” was selected as top one among
ten Frontier hotspots in the eld of chemistry and materials
science.69 Furthermore, the general understanding of the rela-
tionship between chemical composition, physical properties
and energy storage performance is unsatisfactory to this day.
Hence, in this review, the universal design strategies to opti-
mize the energy storage performance and the special tailoring
strategies of each type of material system based on their unique
properties are emphasized, which differentiates this compre-
hensive review from others. Also, we summarize the advances of
This journal is © The Royal Society of Chemistry 2021

Review
different lead-free bulk ceramics for electrical energy storage in
the past ten years accompanied with the development history,
underlying mechanism, chemical modication methods to
improve the energy storage performance and their respective
advantages and disadvantages.
This review has been organized into four parts, as illustrated
in Fig. 3. In the rst part, we provide a general introduction to the
background and applications of dielectric capacitors, the prin-
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ciple of dielectric capacitors for electrical energy storage and
summarize the development history of lead-free ceramics for
energy storage. In the second part, a classication of dielectrics
and their characteristics, key parameters to evaluate the energy
storage performance and the corresponding characterization
methods as well as the universal design strategy to optimize the
energy storage performance are presented. Then, the unique
physical properties and the corresponding design strategies of
each type of dielectric ceramic are presented together with
Fig. 4 (a) Classification of dielectric materials with the corresponding P–E hysteresis loops, 3r–E curves and the domain structure. (b) Schematic
diagram of a bulk ceramic with electrodes and together with the methods to measure and calculate the key parameters for energy storage
properties.
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a summary of their respective advantages and disadvantages. The
challenges and future development direction of dielectric
ceramics for energy storage are summarized at the end of this
review. We hope this review can provide a deeper understanding
of the relationship among chemical composition, physical
properties and energy storage performance of dielectric ceramics,
and attract more research interest to join this eld.
2. Fundamentals and strategy
2.1 Classication of dielectrics and their characteristics
Based on the relationship between the 3r and the applied electrical
eld (E), dielectric materials for energy storage can be classied
into ve kinds, namely, linear dielectrics (LD), normal ferroelec-
trics (FE), relaxor ferroelectrics (RFE), antiferroelectrics (AFE) and
relaxor-antiferroelectrics (RAFE).16,71,72 Fig. 4a displays the polari-
zation–electric eld (P–E) hysteresis loops, 3r–E curves and the
J. Mater. Chem. A

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Table 2 Basic characteristics of five types of dielectric materials
Material types Pr (mC cm2) Pmax (mC cm2) Eb (kV cm1)
LD Zero Small High
FE Large Large Low
RFE Small Medium Medium
AFE Near zero Large Medium
RAFE Small Large High
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corresponding domain structure of different types of dielectrics,
and their basic characteristics are summarized in Table 2.
For linear materials, the 3r is independent of the applied
electric eld. This feature leads to a linear polarization response
behavior, therefore most of the stored energy can be released
and hence contributes to a high efficiency (h). Most polymers,
glass and some ceramics belong to this kind of materials.67,73–76
These materials exhibit a low dielectric loss but also a low 3r due
to the lack of any spontaneous polarization. Consequently,
a high Eb and a low maximum polarization (Pmax) are usually
obtained in linear materials, resulting in a low Wrec. Neverthe-
less, their energy storage performance and dielectric properties
usually show excellent thermal and frequency stability, making
them widely used in analogue to digital conversion and lter
applications. Although the Wrec of linear materials can be further
enhanced through further increasing the Eb, the signicantly
enhanced electronic conduction and space charge effect will
increase dielectric loss, which in turn deteriorates the h.
For normal ferroelectrics, large ferroelectric domains together
with strong dielectric nonlinearity are their typical features.71,72
Upon application of an effective electric eld, the large ferro-
electric domains are aligned along the direction of the external
electric eld, leading to a high Pmax. However, most of the
domains cannot return to their original state aer removing the
electric eld due to the clamping of domain walls, and a large
reverse electric eld is required to achieve a zero polarization,
leading to a large remnant polarization (Pr) and a high coercive
eld (Ec).72,77 So, normal ferroelectrics usually exhibit a square P–
E hysteresis loop, and most of the stored electrical energy cannot
be released, resulting in a low Wrec and a low h.
Relaxor ferroelectric materials usually exhibit different
cations in similar crystallographic sites.78,79 A typical feature of
relaxor ferroelectric materials is dielectric relaxation, namely,
the phase transition occurs over a broad temperature range and
the temperature of maximum 3r (Tm) shis to higher tempera-
ture with the measurement frequency increases.78 Furthermore,
the introduction of other cations in A- or B-sites of the perov-
skite structure generates random elds, which disturbs the
long-rang orders and promotes the formation of polar nano-
regions (PNRs).79 Compared with normal ferroelectric domains,
PNRs exhibit high dynamics, low energy barriers and good
thermal stability, contributing to narrow P–E hysteresis loops
with a low Pr and a high Eb. These characteristics are in favor of
a high h, while the moderate Pmax and strong dielectric
nonlinearity lead to a moderate Wrec. More information about
the physical properties of relaxor ferroelectrics can be found in
several ref. 60, 72, 79 and 80.
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Feature of P–E hysteresis loop Wrec (J cm3) h (%)
No hysteresis Low (<2) High (>90%)
Large hysteresis Low (<0.5) Low (<50%)
Weak hysteresis Moderate (>2) High (>80%)
Medium hysteresis High (>3) Low (<70%)
Small hysteresis Ultrahigh (>4) Moderate (
75%)
Antiferroelectric materials are characterized by the presence
of anti-parallel dipolar alignment at two nearby crystalline
lattices.81 This arrangement results in a zero polarization in their
innate state or before applying an external electric eld. When
the applied electric eld is high enough, an antiferroelectric-to-
ferroelectric phase transition occurs, resulting in a macroscopic
polarization. The induced polarization returns to zero through
the ferroelectric-to-antiferroelectric phase transition when the
applied electric eld is reduced below a certain critical value. Due
to the antiferroelectric-to-ferroelectric and ferroelectric-to-
antiferroelectric phase transition, antiferroelectric materials
exhibit a double P–E hysteresis loop with a nearly zero Pr and
a high Pmax, contributing to a high Wrec. However, the large
hysteresis during the forward and backward ferroelectric-
antiferroelectric phase transition leads to a relatively low h.
More information about the physical properties of antiferro-
electrics can be found in these ref. 60, 72, 82 and 83.
As discussed above, relaxor ferroelectrics exhibit a high h but
a moderate Wrec, while antiferroelectrics possess a high Wrec but
a relatively low h. To combine their respective advantage
together, researchers recently developed relaxor-
antiferroelectric ceramics, which can be obtained by intro-
ducing a relaxor compound to antiferroelectrics to enhance the
relaxor characteristics and induce nanodomains. Compared
with relaxor ferroelectrics, a high Pmax can be expected in
relaxor-antiferroelectric ceramics due to the antiferroelectric-to-
ferroelectric phase transition. Compared with antiferro-
electrics, the features of strong relaxor properties and nano-
domains in relaxor-antiferroelectric ceramics result in a narrow
P–E hysteresis loop, especially for the nearly linear polarization
behavior under low electric elds, contributing to a high h.
Hence, both a high Wrec and a high h can be expected in relaxor-
antiferroelectric ceramics under a high electric eld.
2.2 Key parameters to evaluate the energy storage properties
and their characterization
Wrec is regarded as one of the key parameters to evaluate the
energy storage performance of dielectric materials. A high Wrec
of dielectric materials means more energy can be stored in
a certain volume, which favors miniaturization, lightweight and
low cost when used in consumer electronics and pulsed power
systems. The rst diagram of Fig. 4b shows a schematic of
a bulk ceramic with electrodes, which is used for electrical
measurements. The energy storage performance is usually ob-
tained from the P–E hysteresis loop, which is measured using
a Sawyer-Tower circuit.72 Aer applying a voltage V, the total
energy (U) stored in the ceramic can be calculated by eqn (1):
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ð Qmax Wrec
U¼ VdQ (1) h¼ (8)
0
W

where Qmax is the maximum charge. For dielectric capacitors

with a linear materials, the total energy stored can be expressed High h means that more energy can be released during the
by eqn (2): discharge process, while the unreleased energy usually trans-
forms into thermal waste, which increases the temperature of
1
U¼ CVmax 2 (2) the devices and thereby deteriorates their performance. Nor-
2 mally, better reliability and longer lifetime can be expected in
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where Vmax is the maximum voltage that the capacitor can
withstand before breakdown. The energy stored in per unit
volume, i.e., energy storage density (W), can be expressed by eqn
(3):
Ð Qmax ð Dmax
U VdQ
W¼ ¼ 0 ¼ EdD (3)
Ad Ad 0
where D is the electric displacement, E is the applied electric
eld, d is the distance between the electrodes and A is the area
of the capacitor electrodes. In addition, the polarization (P) and
D satisfy the following relationship:
P ¼ D  30E ¼ 30(3r  1)E (4)
So, for dielectrics with a high 3r, the value of D and P are
basically equal. In this case, eqn (3) could be rewritten as eqn
(5):
ð Pmax
W¼ EdP (5)
0
where Pmax represents the polarization of a dielectric material
under its dielectric breakdown strength (Eb), i.e., the maximum
polarization. However, due to the hysteresis loss, only part of
the stored energy can be released. The recoverable energy
storage density (Wrec) is illustrated by the blue area in the
second schematic diagram of Fig. 4b, which can be calculated
from eqn (6):
ð Pmax
Wrec ¼ EdP (6)
Pr
This leads to the second key parameter of energy storage
performance, namely, efficiency (h). For dielectric materials,
especially for non-linear dielectric materials, the energy stored
during the charging process cannot be completely released. As
the second schematic diagram in Fig. 4b shows, during the
charging process, the polarization gradually increases to Pmax
with E increasing from zero to Eb. The stored total energy is the
sum of the blue and yellow area. During the discharge process,
the polarization decreases from Pmax to Pr with E decreasing
from Eb to zero, and the yellow area in Fig. 4b represents the
energy loss density (Wloss), which can be expressed by eqn (7):
Wloss ¼ W  Wrec (7)
h of dielectric materials is dened as the ratio of released
electrical energy to stored electrical energy during a charging/
discharging process, which can be calculated from eqn (8):
dielectrics with high h.
Thermal stability should also be considered for dielectric
materials, especially for devices working in harsh environ-
mental conditions. For example, the dielectric capacitors used
in underground oil exploration and aircras are working in
a temperature range from 150  C to 200  C and 55  C to 250  C,
respectively. To ensure the reliable operation of these devices,
dielectric materials are required to maintain good energy
storage performance in a wide temperature range. This
parameter is usually obtained by evaluating the variation of Wrec
and h within a temperature range and under a certain electric
eld. Another parameter is fatigue endurance, which is impor-
tant for the long-term reliable operation of the capacitors.
During the repeated charging/discharging processes, the
dielectric and breakdown properties of dielectric materials
deteriorate due to structural defects such as defective dipoles,
vacancies and secondary phases.61 This feature gradually
degenerates the energy storage performance of dielectric
materials, and even leads to material failure. So, the fatigue
endurance also needs to be considered when evaluating the
performance of dielectric materials, which is obtained through
measuring the variation of the Wrec and h aer charging/
discharging for multiple times.
The above mentioned Wrec is usually obtained by assuming
the system is in a quasi-state, which is not completely the same
as the electrical energy that can be released in practical appli-
cations, especially for high frequency discharge processes. To
solve this problem, the dynamic discharge energy density (Wdis)
is measured by a charge–discharge measurement using
a specic circuit, as shown in the third schematic diagram of
Fig. 4b, and this method is more suitable for characterizing the
performance of capacitors. For this measurement, the dielectric
capacitor is rst charged by applying a DC voltage, then the
charged energy is consumed on a load R by a high-speed and
high-voltage switch. To ensure that the measured Wdis is close to
the actual Wdis, the resistance of the load R should be much
larger than that of the equivalent series resistance of the
capacitor, so that most of the stored electrical energy can be
consumed on the load R. Also, the clamping between the large
domains and the existence of viscous force are responsible for
the low value of Wrec in comparison with Wdis, especially for
a high electric eld and a high testing frequency.48,53 Through
recording the current passed through the resistor I(t), the Wdis
can be calculated from eqn (9):
Ð
RI 2 ðtÞdt
Wrec ¼ (9)
Vvol

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Fig. 5 The universal design strategies to obtain high energy storage performance in dielectric materials.

where Vvol is the volume of the dielectric capacitor. Also, the the time required to discharge 90% of the total energy,
two parameters Imax and t0.9 can be derived from the I(t) respectively, as presented in the fourth schematic diagram of
curve, which represent the maximum discharge current and Fig. 4b.

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All in all, although various dielectric materials have been
developed for electrical energy storage, their performance is still
relatively low. Especially for the Wrec and h, dielectric ceramics
with both a high Wrec (>4 J cm3) and a high h (>90%) are still in
high demand to meet the requirements for integration in
electronic devices. To achieve this goal, it is urgent to nd
effective design strategies to develop high-performance dielec-
tric materials for energy storage applications.
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2.3 Universal design strategies
According to eqn (6)–(8), an ideal dielectric should simulta-
neously exhibit the characteristics of a large Pmax, a low Pr and
a high Eb to achieve both a high Wrec and a high h. The polar-
ization and Eb of dielectric materials are affected by many
factors, which provide a wide choice to optimize the energy
storage performance, as shown in Fig. 5.
Eb is the maximum electric eld that a dielectric material can
sustain before breakdown. There are mainly three types of
breakdown processes: intrinsic breakdown, partial discharge
breakdown and thermal breakdown.48,84 Intrinsic breakdown
can result from electronic breakdown and avalanche break-
down. Electronic breakdown is a transition process of electrons
from valence band to conduction band under a sufficiently high
electric eld, while avalanche breakdown is caused by the
instant accumulation of large amounts of carriers when they
obtain enough energy to exceed the ionization potential.
Although dielectric materials usually exhibit a high intrinsic
breakdown strength, partial discharge breakdown or thermal
breakdown usually occur rst before the intrinsic breakdown
strength is reached. Dielectric material is an inhomogeneous
medium, composed of grains, grain boundaries, pores and
other impurities. This leads to an uneven electric eld distri-
bution inside the dielectric material upon application of an
external electric eld. Some areas, sustaining high electric eld
but possessing low withstand voltage, will produce partial
discharge and fail rst, which will destroy the insulation
performance of the dielectric material and then leads to the
partial discharge breakdown. Meanwhile, under an external
electric eld, conductance and non-displacement polarization
will convert part of the electrical energy into Joule heat. When
the heat generation rate is higher than the heat dissipation rate,
heat will accumulate inside the material, eventually leading to
thermal breakdown.85 According to the mechanism of different
breakdown processes, the Eb of dielectric materials can be
enhanced from both intrinsic factors and extrinsic factors.
For intrinsic breakdown, it is mainly affected by intrinsic
factors, and high Eb could be obtained by increasing the band
gap or enhancing the phonon frequency.46,86,87 Large band gaps
imply that a high energy, i.e. a large applied electric eld, is
required to promote electrons from the valence band to the
conduction band, while a high phonon frequency indicates
a high electron–phonon collision frequency and hence a quick
energy loss rate, contributing to a high intrinsic breakdown
strength.46
Discharge breakdown and thermal breakdown characteris-
tics are affected by both intrinsic and extrinsic factors. For
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intrinsic factors, the Eb of dielectrics could be improved by
tailoring the dielectric loss, grain size, porosity and grain
boundary, etc.32,88–91 Large dielectric loss is a key factor for
thermal breakdown, since it generates a large amount of Joule
heat during the charge and discharge processes. For bulk
ceramics, dielectric loss mainly comes from the space charge of
the impurity phase, impurities, the electronic conductivity of
vacancy related-defects and unstable cations (Ti4+ 4 Ti3+, Fe3+
4 Fe2+). To suppress the dielectric loss, the commonly used
method is to optimize the sintering process, such as buried
powder sintering and protective atmosphere sintering or by
adding loss inhibitors such as MnO2. For grain size effects,
previous research revealed that the Eb and the grain size obey
the following relationship:92,93
Eb f Ga (10)
where G is the average grain size and a is in the range of 0.2–0.4.
The increased Eb as the grain size decreases can be explained
from the following two aspects. Polycrystalline ceramics are
composed of grains and grain boundaries. Grain boundaries
may act as the barrier regions between two grains and exhibit
a higher resistivity than that of grains. As the grain size
decreases, the grain boundary density increases, enhancing the
insulation properties and relaxation activation energy of the
dielectrics.94,95 Also, pores and grains possess a comparable size
in polycrystalline ceramics, hence the pore size decreases as the
grain size becomes small. Dielectric breakdown usually occurs
rst at the position of defects such as pores and impurities, due
to their low withstand voltage. In comparison with large pore
size, small pore size can reduce the local voltage applied on the
pore, reducing the possibility of partial discharge breakdown.96
In addition, good uniformity of the grain size favors a uniform
distribution of the applied electric eld, contributing to a high
Eb.97 Considering this, a lot of studies were carried out to
decrease the grain size and improve their uniformity to obtain
a high Eb through composition engineering and optimizing
fabrication processes. For polycrystalline ceramics, pores
cannot be avoided, especially for ceramics prepared by
conventional solid state methods. To reduce the porosity, the
methods currently adopted are liquid-phase sintering and
pressure assisted sintering. For liquid-phase sintering, the
added sintering aids (ZnO, CuO, Bi2O3 and glass) exhibit a low
melting point in comparison with the matrix material. These
sintering aids form a liquid phase during the sintering process
and then promote the mass transportation process, generating
a fast densication and a high density. The pressure assisted
sintering methods mainly include spark plasma sintering and
hot pressed sintering. A common feature of these methods is
the assistance of external pressure during the sintering process,
which is conducive to the contact diffusion and the mass
transportation of particles, and hence a denser microstructure.
Furthermore, a high Eb can be obtained through increasing the
resistivity of the grain boundaries. The rst method is to
introduce some interlayers like Al2O3, SiO2 and glass to coat the
ceramics and then form a core–shell structure. These coating
layers with a high Eb and a low dielectric loss sustain most of the
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Journal of Materials Chemistry A
electric eld when an external electric eld is applied, thereby
weakening the electric eld applied on the ceramics cores. Also,
the coating layer suppresses the dielectric loss and inhibits the
grain growth of the core. So, an enhanced Eb can be expected in
those ceramics with core–shell structure.98–101 The other method
is to introduce a secondary compound with high Eb to form
composite materials. The most used secondary compound is
MgO due to its large band gap and low diffusion rate.102–104 A fast
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diffusion rate makes the secondary phase react easily with the
matrix material to form impurity phases. In the composite
material, the second phase usually aggregates at the grain
boundaries of the matrix and acts as a breakdown barrier,
contributing to a high Eb.
The Eb of dielectric materials is also inuenced by extrinsic
factors, such as electrode type/size, sample thickness and test
condition (type of voltage, testing medium, testing frequency
and testing temperature).105–108 For example, compared with
small-size electrodes, ceramics with large-size electrodes are
more prone to breakdown.109–111 For dielectrics, the breakdown
location is oen near the edge of the electrode and large-area
electrodes provide more defect places for the breakdown.
Also, the quality and surface smoothness become worse as the
area of the electrode increases, which affect the electric eld
distribution and can induce partial discharge breakdown.
Therefore, dielectric ceramics with large-area electrodes usually
show a low Eb. Meanwhile, compared with the high-temperature
electrode, the interface contact between the sample and the
room-temperature electrode is not very good, resulting in
a larger interface loss and a low Eb. Furthermore, the Eb of
dielectric ceramics is dependent on the thickness of the sample,
namely, Eb increases as the sample thickness decreases. For
a thinner dielectric ceramic, fewer defects exist and faster heat
dissipation rate between the dielectric material and the envi-
ronment can be expected, contributing to a higher Eb. There-
fore, lms and MLCC usually exhibit a high Eb due to the low
thickness, resulting in a high Wrec. Apart from the quality of the
fabricated ceramic, there may be some differences in sample
thickness and testing condition. For example, as the 3r of the
test medium increases or the testing frequency becomes lower,
the measured Eb of dielectrics will increase. So, the Eb value of
the same dielectric material in different references is slightly
different. Considering this, the specic sample congurations
(sample thickness, electrode size) and test conditions (type of
voltage, testing medium) should be reported and emphasized in
future research. In addition, a standard testing procedure is
highly needed.
For dielectric materials, there are ve types of polarization,
namely, electronic polarization, atomic polarization, dipolar
polarization, ionic polarization and interfacial polarization.67,112
On the one hand, electronic, atomic and ionic polarization
belong to the resonance phenomena, which originate from the
very slight displacement of the electrons, nuclei and ions under
the action of an external electric eld, respectively. These forms
of polarization exist in all dielectrics and they do not contribute
to dielectric loss in the power and radio frequencies since their
dielectric losses are located in the infrared and optical
frequencies. On the other hand, dipolar and interfacial
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polarization belong to the relaxation phenomena. For some
dielectric materials, the positive and negative charge centers of
the unit cell do not coincide depending on the crystal structure,
namely, the unit cell itself has a certain dipole moment. Under
an electric eld, these dipole moments will turn and align in the
direction of the external electric eld to form dipolar polariza-
tion, which usually takes place in the range between 1 Hz and
100 MHz. Interfacial polarization refers to charge carriers
accumulated at the interfaces of different materials in the
composites, and it takes a long time to release these charges
from hours to years. These two polarization types contribute to
both the 3r and the dielectric loss in the power and radio
frequencies, and their contribution varies with temperature and
frequency.
To achieve a large DP, both a high Pmax and a low Pr are
required. Using the Pb–O hybridization, lead-based ceramics
usually exhibit a higher Pmax than that of lead-free
ceramics.113,114 Bi3+ is isoelectronic with Pb2+ and the hybrid-
ization between the Bi 6p and O 2p orbitals is expected to
improve the polarity of A-site ions, contributing to a high Pmax.
Based on this, various Bi-based compounds were used to tailor
the properties of matrix materials and some high energy storage
performances have been achieved.115–119 Also, the existence of A-
site vacancies is conducive to increasing the 3r and then
generating a high Pmax.120,121 Furthermore, according to eqn (4),
the polarization should increase linearly as the applied electric
eld increases. However, the strong dielectric nonlinearity of
dielectrics makes the polarization tend to saturate early,
limiting the further increase of Wrec under high electric elds.
Considering this, decreasing the dielectric nonlinearity or
delaying the polarization saturation should be another good
option to improve the energy storage performance despite the
fact that the value of Pmax is not enhanced, which could be
achieved through chemical modication or rening
grains.122–125 In addition, a large DP can be obtained through
engineering the domain structure.126–128 For large ferroelectric
domains, their arrangement along the direction of the external
electric eld can produce a high Pmax. However, some of the
switched large domains cannot return to their original state
aer removing the electric eld, resulting in a large Pr. So,
dielectric ceramics with large ferroelectric domains usually
exhibit a large Pmax and a large Pr, generating a small DP.
Compared with large ferroelectric domains, polar nanoregions
(PNRs) and nanodomains possess low energy barriers and high
dynamics. In this case, most of the switched domains can revert
to their original state aer removing the electric eld, contrib-
uting to a low Pr.129–131 Also, upon an effective electric eld,
a moderate Pmax can be expected in dielectric materials with
PNRs and nanodomains. Therefore, dielectric materials with
PNRs and nanodomains usually exhibit a moderate Pmax and
a low Pr, contributing to a high DP. If the domain size is further
decreased or no domain structure exists in the dielectric
materials, although the Pr can be further decreased, the Pmax is
also very low because of the lack of dipoles, which results in
a low DP. Consequently, many studies have been carried out to
design dielectric materials with PNRs or nanodomains to obtain
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Fig. 6 The design strategies to improve the energy storage performance of ST ceramics: (a) increasing Pmax and (b) increasing Eb.
a large DP. Also, low dielectric loss is benecial to a slim P–E
hysteresis loop, and hence a low Pr.
In general, the energy storage performance of dielectrics is
affected by many factors and some of them are mutually
exclusive. For example, a high 3r and a large Eb are conducive to
a high energy storage performance. However, the negative
correlation between 3r and Eb makes dielectrics with a high 3r
possess a low Eb and vice versa.48,132,133 In addition, a large Wrec
can be obtained under a high electric eld. However, the
dielectric loss also increases as the applied electric eld
increases, which inevitably damages the h.122,133 These charac-
teristics make the research on dielectrics for electrical energy
storage more interesting and challenging. In the following part,
the specic tailoring strategies and energy storage properties of
each type of material are summarized based on their unique
physical characteristics.
3. Linear ceramics
3.1 SrTiO3 (ST)-based ceramics
3.1.1 Physical properties and design strategies. As a typical
perovskite material, ST has been widely used in electronic
devices, due to its low dielectric loss, excellent thermal stability
and wide band gap (3.4 eV). At around 120  C, it undergoes
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a ferroelectric phase transition with a high permittivity (
104),
and at room temperature it exhibits a paraelectric phase.134,135
Although pure ST possesses a high Eb (
250 kV cm1) due to its
low dielectric loss, the low 3r around room temperature together
with the lack of spontaneous polarization results in a low Pmax
(
8 mC cm2), limiting its applications for electric energy
storage. These features lead to a low Wrec (
1.0 J cm3) of pure
ST in spite of a large h (>90%).136,137 Currently, there are mainly
two methods to improve the Wrec of ST ceramics: (1) increasing
the Pmax and (2) further increasing the Eb, as shown in Fig. 6.
3.1.2 Design strategy of improving maximum polarization.
To improve the Pmax of ST ceramics, the commonly used
methods are introducing other ions to form a new solid solution
or designing layered structures with ceramics possessing a high
3r.138–146 Table 3 summarizes the energy storage properties of ST-
based bulk ceramics through enhancing the polarization. For
example, Yang et al. adopted BNT and Ba0.94La0.04Zr0.02Ti0.98O3
to tailor the dielectric properties of ST ceramics, and a tape-
casting process was employed to prepare high-quality
ceramics, as shown in Fig. 7a.147 It was found that the incor-
poration of BNT and Ba0.94La0.04Zr0.02Ti0.98O3 signicantly rai-
ses the phase transition temperature, leading to a high 3r at
room temperature, as shown in Fig. 7b. Beneting from the
increased 3r, the Pmax of ST-based ceramics was signicantly
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Table 3 Summary of energy storage properties of ST-based bulk ceramics through enhancing the maximum polarization

Composition Wrec (J cm3) h (%) Pmax (mC cm2) Pr (mC cm2) Eb (kV cm1) 3r Ref.

ST 0.7 210 136

0.6ST-0.4BNT 1.7 69.9 25.4
4 210 3000 151
0.5ST-0.5(0.95BNT-0.05BaAl0.5Nb0.5O3) 1.89 77 30.6
3 190 2800 152
0.8ST-0.2(0.93BNT-0.07Ba0.94La0.04Zr0.02Ti0.98O3) 2.83 85 23.9
1.5 320 1600 153
0.9ST-0.1(Bi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3) 2.59 85 21
1.6 323 900 154
0.6ST-0.4Bi0.5(Na0.82K0.18)0.5Ti0.96Zr0.02Sn0.02O3 1.45 86 24
1.3 167 2300 145
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0.7ST-0.3(0.65BT-0.35BNT) 1.4 90 17.1 0.4 196 1100 144

0.45ST-0.2NBT-0.35BT 1.78 77 29.2 3 170 1050 143
0.9ST-0.1(0.93BNT-0.07Ba0.94Sm0.04Zr0.02Ti0.98O3) 1.93 80 13.3
2 420 580 138
0.88ST-0.02CaZrO3-0.1MgTiO3 + BaCu(B2O5) 1.05 98.8 287.8 311 155
0.9(Sr0.7Bi0.2)TiO3-0.1Bi(Mg0.5Hf0.5)O3 3.1 93
23
0.5 360 840 140
(ST + Li2CO3)/(0.94Bi0.54Na0.46TiO3-0.06BT) 2.41 68 36 5.3 237 2600 142
(ST + 0.5 wt% Li2CO3)/(0.93BNT-0.07Ba0.94La0.04Zr0.02Ti0.98O3) 2.72 74 29 7.5 294 900 139

improved accompanied with a slightly deteriorated Eb (see
Fig. 7c). An optimal energy storage performance was achieved in
0.8ST-0.2(BNT-Ba0.94La0.04Zr0.02Ti0.98O3) with a Wrec of 2.83 J
cm3 and a h of 85%. It should be noticed that enhanced
polarization behavior can also be achieved in ST-based ceramics
through incorporating single high valence cations such as Bi3+,
La3+ and Pr3+ due to the ionization of oxygen vacancies.140,148,149.
For example, a high Wrec of 3.1 J cm3 was achieved in Bi-
modied ST-based ceramics.140 Apart from constructing new
solid solutions, Yan et al. proposed a strategy of fabricating

Fig. 7 (a) Schematic diagram of the tape-casting process. (b) Temperature dependence of dielectric properties and (c) P–E hysteresis loops of
(1  x)ST-x(BNT-Ba0.94La0.04Zr0.02Ti0.98O3) ceramics. (d) Simulation of the dielectric breakdown process of the (ST + Li2CO3)/(0.94Bi0.54-
Na0.46TiO3-0.06BT) layered structure. (e) P–E hysteresis loops of STL ST + Li2CO3 ceramics, 0.94Bi0.54Na0.46TiO3-0.06BT ceramics and (ST +
Li2CO3)/(0.94Bi0.54Na0.46TiO3-0.06BT) ceramics at room temperature and under different electric fields. (a)–(c) Reprinted with permission from
ref. 147 Copyright 2017 American Chemical Society. (d) and (e). Reproduced from ref. 150 with permission from The Royal Society of Chemistry.

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Table 4 Summary of energy storage properties of ST-based bulk ceramics through improving the Eb
Composition Wrec (J cm3) h (%) Pmax (mC cm2)
ST 0.7
ST + (Bi2O3$3TiO2) 1.63
23
ST + BaCu(B2O5) 1.05 98.8
ST + SiO2 1.155
5.8
ST + ZrO2 1.62
Sr0.92Dy0.08TiO3 4 89.5 17.5
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a layered structure to combine the high Eb of ST and the large 3r
of other materials together.139,150 For example, a (ST + Li2CO3)/
(0.94Bi0.54Na0.46TiO3-0.06BT)-based multilayer structure was
fabricated via a tape-casting and laminating technique. Finite
element analysis was adopted to simulate the breakdown
process of the layered structure, as displayed in Fig. 7d. It was
found that the electrical trees start from the 0.94Bi0.54Na0.46-
TiO3-0.06BT layer due to its low Eb, while the ST + Li2CO3 layer
acts as a barrier because of its high electric insulation, which
weakens the pace of electrical trees. As a result, a higher Eb than
0.94Bi0.54Na0.46TiO3-0.06BT ceramics was achieved in the
layered structure (see Fig. 7e). Beneting from the high 3r of
0.94Bi0.54Na0.46TiO3-0.06BT, the Pmax of the layered structure
was also signicantly enhanced in comparison with ST + Li2CO3
ceramics (see Fig. 7e). Hence, the advantages of ST + Li2CO3 and
0.94Bi0.54Na0.46TiO3-0.06BT are simultaneously integrated in
the layered structure, resulting in a large Wrec of 2.41 J cm3
under 237 kV cm1.
3.1.3 Design strategy for improving the dielectric break-
down strength. Some researchers try to further improve the Eb
to enhance the Wrec of ST ceramics. The method mostly used is
introducing sintering aids or suitable oxides to optimize the
microstructure and reduce the number of defects. Table 4
presents the energy storage performance of ST-based bulk
ceramics through improving the Eb. For example, Wang et al.
found that the addition of ZrO2 renes the grain size, forming
more grain boundaries. Due to the high insulation of the grain
boundaries, the Eb was improved from 201 kV cm1 of pure ST
ceramics to 289 kV cm1 of ST + 0.4 mol% ZrO2 ceramics,
leading to an enhanced Wrec of 1.62 J cm3.156 Recently, Dy ions
were adopted by Guo et al. to improve the Eb of ST ceramics.157
Fig. 8 (a) A comparison of the Wrec achieved in ST-based ceramics through improving the Pmax or enhancing the Eb. (b) 3r as a function of Eb of
ST-based ceramics.
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Pr (mC cm2) Eb (kV cm1) 3r Ref.
210 136

5 217.6 870 161
287.8 311 155

2 361 160 162
289 300 156

1 510 350 157
The incorporation of suitable Dy ions increased the insulation
of grain boundaries and reduced carrier mobility because the
formed defect dipoles suppress the movement of oxygen
vacancies and then reduce the ion conductivity. However, an
excessive number of Dy ions deteriorates breakdown perfor-
mance due to the introduced free electrons through
substituting the Sr position. As a result, the optimal Wrec was
achieved in Sr0.92Dy0.08TiO3 ceramics with a value of 4 J cm3
under 510 kV cm1. It is also an effective method to improve Eb
of ST ceramics by combining oxides and polymers with high
withstand voltage to construct core–shell structures and nano-
composite materials, respectively.158–160
3.1.4 Summary of ST-based ceramics. In summary, the
energy storage performance of ST-based ceramics has been
signicantly enhanced by further improving the Pmax or Eb.
These materials usually show a high h, while their Wrec values
are still below 4 J cm3. Fig. 8a presents the energy storage
performance of ST-based ceramics. In comparison, improving
Pmax is more effective than increasing Eb to obtain a large Wrec.
This situation can be ascribed to the fact that pure ST ceramic
already exhibits a relatively high Eb, while its small 3r leaves
a large room for improvement. In contrast, a high 3r of ST-based
ceramics is usually obtained at the cost of Eb, and vice versa,
namely, a negative correlation between the 3r and the Eb, as
displayed in Fig. 8b.163–166 In these results, we found that
a moderate 3r (
1000) and a moderate Eb (
350 kV cm1) are
more in favor of a high energy storage performance, as shown in
the blue shade in Fig. 8b. This feature provides a guidance to
further optimize the energy storage performance of ST-based
ceramics in future research. For practical applications, the
low dielectric loss, good thermal stability and excellent
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frequency stability endow ST-based ceramics with great promise
in the devices requiring high stability and reliability.
3.2 CaTiO3 (CT)-based ceramics
3.2.1 Physical properties and design strategies. CT is
another promising linear dielectric for energy storage because
of its large band gap (3.4 eV) and low dielectric loss
(
105).167–169 Its intrinsic dielectric strength is predicted to be
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enhanced from 435 kV cm1 of conventional solid state method
fabricated CT to 1188 kV cm1 of SPS prepared CT with alumina
blocking layer, as shown in Fig. 9c, leading to a high Wrec of 11.8
J cm3. Also, the dielectric breakdown process was investigated
from a microscopic viewpoint. It was found that the breakdown
is caused by the rapid increase of localized temperature,
namely, thermal breakdown, which can be optimized through
decreasing the electrical conductivity and increasing the

thermal conductivity. Apart from optimizing the microstruc-

around 4200 kV cm1, while the low 3r (
175) makes pure CT
show a relatively low Wrec (
1.5 J cm3).166,170 The design
strategy of CT is similar to that of ST ceramics, namely,
increasing the 3r or enhancing the Eb. For example, spark
plasma sintering (SPS) was adopted to fabricate pore-free
ceramics with small grain size. As shown in Fig. 9a and b, the
grain size and porosity were obviously decreased in comparison
with the ceramics prepared by the conventional solid state
method. Meanwhile, an alumina blocking layer was introduced
between the electrodes and CT to further improve the Eb
through accelerating the heat dissipation. As a result, the Eb was
ture, Zhang et al. proposed another method of local structure
design to improve the Eb of CT ceramics.171 For CT ceramics, the
unstable Ti4+ ions and the relatively rigid chemical bonds of
A–O–B also worsen the breakdown performance. To solve this
problem, Sm3+ ions were incorporated into CT to generate A-site
vacancies. The introduced A-site vacancies not only stabilize the
valence state of Ti4+ ions, but also provide sufficient space to
tolerate the off-center displacement of Ti cations in TiO6 octa-
hedra under external electric elds (see Fig. 9d). As a result, the
Eb gradually increases with increasing Sm concentration and
the maximum Wrec is achieved in Ca0.97Sm0.02TiO3 ceramics

Fig. 9 SEM images on polished and thermally etched surfaces of (a) conventional solid state method fabricated CT samples and (b) SPS method
fabricated CT samples. (c) Weibull distribution of DC dielectric strength of CT ceramics prepared by different methods. (d) Local structures
around the dopants Sm3+ and A-site vacancy in Ca11.5xSmxTiO3 ceramics. (e) Weibull distribution of the Eb of Ca11.5xSmxTiO3 ceramics. (f) Wrec
and h values of Ca11.5xSmxTiO3 ceramics. (a)–(c) Reprinted with permission from ref. 170. Copyright 2017 John Wiley and Sons. (d)–(f) Reprinted
with permission from ref. 171. Copyright 2020 Elsevier.

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Table 5 Summary of energy storage properties of CT-based bulk ceramics

Composition Wrec (J cm3) h (%) Pmax (mC cm2) Pr (mC cm2) Eb (kV cm1) 3r Ref.

CT 1.5 435 176 166

CaZr0.4Ti0.6O3 2.7 720 120 166
Ca0.97Sm0.02TiO3 2.0 93.7 547 167 171
CT (SPS) 6.9 910 189 170
0.8CT-0.2CaHfO3 9.0
17
1 1200 198 172
0.8CT-0.2CaHfO3 + MnO2 9.5
17
0.5 1300 196 172
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0.9CT-0.1BiScO3 1.55 90.4 12.4
0 270 170 173

Table 6 Summary of energy storage properties of BT-based ferroelectric ceramics

Composition Wrec (J cm3) h (%) Pmax (mC cm2) Pr (mC cm2) Eb (kV cm1) 3r Ref.

Ba0.7Ca0.3TiO3 0.24 61 17.5 2.2 50 185

BaZr0.1Ti0.9O3 0.5
14
3 30 2998 181
Ba0.9995La0.0005TiO3 0.342 39.1 21.6 3.1 65 9000 187
Ba0.97Sm0.02Zr0.15Ti0.85O3 1.15 92 38.7 1.9 100 9500 188
0.85Ba(Zr0.2Ti0.8)O3-0.15(Ba0.7Ca0.3)TiO3 0.68 72 170 8400 186
BaTi0.85Sn0.15O3 + MgO 0.51 92.2
10
0.5 190 1586 102
BT + BaO-SrO-TiO2-Al2O3-SiO2-BaF2 0.32
24
7 88 4000 189

with a value of 2 J cm3, as shown in Fig. 9e and f. In addition,
an enhanced Wrec of CT ceramic was also realized through
incorporating BiScO3 to improve the Pmax. A high Pmax of 12.36
mC cm2 was achieved in 0.9CT-0.1BiScO3 ceramics, which is
about 4.6 times higher than that of pure CT ceramics, leading to
a high Wrec of 1.55 J cm3. First-principles calculations revealed
that the increased Pmax comes from the atomic displacement of
Ti ions due to the Sc substitution.
3.2.2 Summary of CT-based ceramics. Table 5 summarizes
the energy storage performance of CT-based ceramics. As
shown, these ceramics show a high Eb but a low DP. Although
a large Wrec is realized in some compositions, the high Wrec is
usually obtained under a ultrahigh electric eld beneting from
the high Eb. However, the ultrahigh electric eld is challenging
for the charging circuit in practical applications and additional
insulation measures are needed to protect surrounding
components. Also, the high Eb of these samples is usually
achieved through advanced sintering methods, optimizing the
testing condition or decreasing thickness, which are difficult to
use in commercial production. For CT-based ceramics, the
small DP is the key limiting factor in achieving a high Wrec due
to the low 3r, while the related research is limited to date.
Consequently, improving the dielectric constant through
chemical modication or structural design would be a good
choice to further optimize the energy storage performance of
CT-based ceramics in future research.
4. Relaxor ferroelectric ceramics
4.1 BaTiO3 (BT)-based ceramics
4.1.1 Physical properties. Due to the simple crystal struc-
ture and the rich phase diagram, BT has been considered as
a promising ferroelectric material since its rst discovery in
1946.174 At room temperature and ambient pressure, BT exhibits
a tetragonal phase with the lattice parameters of a ¼ 3.99095 Å
and c ¼ 4.0352 Å. Upon heating at ambient pressure, BT
undergoes a series of phase transitions: rhombohedral (R3m)
/ orthorhombic (Amm2) / tetragonal (P4mm) / cubic
(Pmm).175 During the phase transitions, signicant anomalies in
thermal, mechanical and piezoelectric properties can be
observed, which are exploited for various devices. Apart from
the widely studied piezoelectric effect, electrostrictive effect and
electrocaloric effect, BT-based ceramics also received consider-
able attention for electrical energy storage due to their low
dielectric loss, high 3r and medium Eb.77,176–178 However, the
square P–E hysteresis loop makes pure BT unsuitable for elec-
tric energy storage, showing a low Wrec, a low h and a small Eb.
To improve its energy storage performance, several strategies
have been employed such as composition modication, surface
coating or fabricating ceramic/polymer composites. Here, we
review the BT-based ceramics for energy storage from the
following three aspects: BT-based ferroelectric ceramics, BT-
based paraelectric ceramics and BT-based relaxor ferroelectric
ceramics.
4.1.2 BT-based ferroelectric ceramics. Near the phase
transition from tetragonal to cubic, pure BT ceramic exhibits
a large 3r around 10 000, contributing to a high Pmax. However,
this phase transition occurs at about 120  C, narrowing the
practical applications. Through chemical modication, such as
doping Ca2+ and Ti4+ ions, this phase transition temperature
can be adjusted to around room temperature, while maintain-
ing a relatively high 3r.179–186 However, the large hysteresis loss
and the high leakage current result in a low Eb (<100 kV cm1),
limiting the Wrec. As a result, the Wrec achieved in Ba0.7Ca0.3TiO3
and BaZr0.1Ti0.9O3 ceramics are only 0.24 J cm3 and 0.5 J cm3,
respectively. Table 6 summarizes the energy storage properties
of BT-based ferroelectric ceramics. To further improve the Eb,
BT/glass core–shell nanoparticles were prepared by Su et al.100

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Fig. 10 (a) Schematic diagram of a sol-precipitation method to fabricate BT/glass core–shell nanoparticles. (b) P–E hysteresis loops of coarse-
grained BT/Bi2O3–B2O3–SiO2 (C-BT) and BT/Bi2O3–B2O3–SiO2 nanocomposite (Bi-BT) with a thickness of 16 mm. (a)–(d) Reproduced from ref.
100 with permission from The Royal Society of Chemistry.
As Fig. 10a shows, nanoparticles with core–shell structure can
be obtained aer a series of steps including ultrasonic disper-
sion, magnetic stirring and centrifugation. Transmission
electron microscopy revealed that the shell thickness of the
core–shell nanostructures can be tailored from 9 nm to 2–3 nm
through decreasing the concentration of the glass, as shown in
Fig. 10c and d. Meanwhile, the introduced glass decreases the
sintering temperature due to the low melting of the glass and
the formed shell structure inhibits the grain growth, leading to
a dense microstructure with nanoscale grain size. As a result,
a high Eb of 1140 kV cm1 together with a large Wrec of 10 J cm3
was achieved in BT/Bi2O3–B2O3–SiO2 ceramics with a thickness
of 12 mm (see Fig. 10b).
4.1.3 BT-based paraelectric ceramics. Ba1xSrxTiO3 can be
prepared in all ratios as a solid solution of ferroelectric BT and
paraelectric SrTiO3 (ST). With increasing ST concentration,
Ba1xSrxTiO3 changes from normal ferroelectric to quantum
paraelectric, accompanied by an obvious decrease of the Curie
temperature and the dielectric loss, as shown in Fig. 11a.190,191
Also, theoretical calculations and experimental results revealed
that the P–E hysteresis loop of Ba1xSrxTiO3 ceramic gradually
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changes from square to slim as the concentration of ST
increases (see Fig. 11b and c).192–194 Through carefully tailoring
the concentration of ST, a moderate 3r (
1000) with good
stability, a low dielectric loss, a relatively high Eb (
150
kV cm1) and a slim P–E hysteresis loop could be achieved in
Ba1xSrxTiO3 ceramic, demonstrating great potential in high
energy storage applications. Fletcher et al. predicted that the
Wrec of Ba1xSrxTiO3 ceramic could go up to 8 J cm3 under 1000
kV cm1.195 However, the current Wrec achieved in Ba1xSrxTiO3
ceramic is still relatively low due to the low Eb value. Table 7
summarizes the energy storage properties of BT-based para-
electric ceramics. For example, Wu et al. investigated the
inuence of Sr/Ba ratio on the energy storage properties of
Ba1xSrxTiO3 ceramics and found that the highest Wrec was
achieved in Ba0.4Sr0.6TiO3 ceramic with a value of 0.3629 J
cm3.196 Therefore, the study of Ba1xSrxTiO3 ceramics for
electrical energy storage mainly focuses on Ba0.4Sr0.6TiO3
ceramic. To improve the Eb of Ba0.4Sr0.6TiO3 ceramic, different
strategies were adopted such as optimizing the preparation
process or introducing a second compound with a high Eb. For
instance, Song et al. found that the grain size of Ba0.4Sr0.6TiO3
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Fig. 11 (a) Temperature dependence of 3r and dielectric loss at 10 kHz of Ba1xSrxTiO3 ceramics prepared by microwave sintering. (b) Predicted
P–E hysteresis loops of Ba1xSrxTiO3 single crystals at room temperature under 300 kV cm1. (c) P–E hysteresis loops of BaxSr1xTiO3 ceramics
with varying Sr/Ba ratio. Scanning electron micrographs (SEM) of (d) Ba0.4Sr0.6TiO3, (e) 70 wt% Ba0.4Sr0.6TiO3-30 wt% MgO, (f) Transmission
electron microscope images of Ba0.4Sr0.6TiO3 powders and SiO2 coating Ba0.4Sr0.6TiO3 powders. (g) Frequency dependence of 3r and dielectric
loss at room temperature for (100x) wt% Ba0.4Sr0.6TiO3-x wt% MgO ceramics. (h) Frequency dependence of 3r and dielectric loss for Ba0.4-
Sr0.6TiO3 ceramics with different glass-ceramics contents. (i) P–E hysteresis loops for Ba0.4Sr0.6TiO3 ceramics with different glass-ceramics
contents. (a) Reprinted with permission from ref. 191. Copyright 2013 Elsevier. (b) Reprinted from ref. 192, with the permission of AIP Publishing.
(c) Reprinted with permission from ref. 194. Copyright 2014 Elsevier. (d) and (e) Reprinted with permission from ref. 198. Copyright 2009 John
Wiley and Sons. (f) Reproduced from ref. 203 with permission from The Royal Society of Chemistry. (g) Reprinted with permission from ref. 103.
Copyright 2014 Elsevier. (h) and (i) Reprinted with permission from ref. 201. Copyright 2013 Elsevier.

Table 7 Summary of energy storage properties of BT-based paraelectric ceramics

Composition Wrec (J cm3) h (%) Pmax (mC cm2) Pr (mC cm2) Eb (kV cm1) 3r Ref.

Ba0.4Sr0.6TiO3 0.3629
9
1 90.6 998 196

Ba0.4Sr0.6TiO3 + MgO 1.5 88.5 12.5 0.6 300 950 103
Ba0.3Sr0.7TiO3 + ZnO 3.9 400 610 204
Ba0.4Sr0.6TiO3 + Al2O3 + SiO2 5.09 493 473 203
Ba0.4Sr0.6TiO3 + SrO-B2O3-SiO2 0.44 67.4
10
3.5
90 600 199
Ba0.4Sr0.6TiO3 + BaO-TiO2-SiO2 0.61 143 668 201
Ba0.4Sr0.6TiO3 + Bi2O3-B2O3-ZnO 0.62
8.5
0.5 145 680 202
Ba0.4Sr0.6TiO3 + BaO-B2O3-SiO2-Na2CO3- 0.72 280.5 1300 200
K2CO3

ceramic could be tailored from 5.6 mm to 0.5 mm through
adjusting the sintering process, resulting in an enhanced Eb
from 114 kV cm1 to 243 kV cm1.88 Next, the addition of
a second compound such as MgO, ZnO and glass can also
optimize the microstructure of Ba0.4Sr0.6TiO3 ceramic, leading
to a high Eb.197 Specially, the addition of MgO not only inhibits
the grain growth but also decreases the dielectric loss and
thereby a high Eb of 331 kV cm1 was achieved in 0.7Ba0.4-
Sr0.6TiO3-0.3MgO ceramics, resulting in a Wrec of 1.14 J cm3, as
shown in Fig. 11d and e.198 On this basis, Huang et al. adopted

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Fig. 12 Schematic diagram of the tailoring strategy for BT-based relaxor ferroelectrics.

Table 8 Summary of energy storage properties of BT-based relaxor ferroelectric ceramics

Composition Wrec (J cm3) h (%) Pmax (mC cm2) Pr (mC cm2) Eb (kV cm1) 3r Ref.

0.9BT-0.1(Bi0.9Na0.1)(In0.8Zr0.2)O3 1.33 88
22
1 180 2200 211

0.85BT-0.15Bi(Zn2/3Nb1/3)O3 0.79 93.5 131 212
0.88BT-0.12Bi(Mg0.5Ti0.5)O3 1.81 88
22
0.5 224 1600 37
0.6BT-0.4Bi(Mg0.5Ti0.5)O3 4.49 93
42.5
2 340 875 210
0.9BT-0.1Bi(Mg2/3Nb1/3)O3 1.13 95.8 16.5
0.5 113.5 1509 207
0.875BT-0.125Bi(Mg2/3Nb1/3)O3 1.89 83 19.7 1.2 240 1050 213
0.94BT-0.06Bi2/3(Mg1/3Nb2/3)O3 4.55 92
27
1 520 1750 115
0.85BT-0.15Bi(Mg0.5Zr0.5)O3 2.9 86.8
23
1 280 1000 208
0.85BT-0.15Bi(Mg0.5Zr0.5)O3 1.25 95
15
0 185 920 214
0.88BT-0.12Bi(Mg2/3Ta1/3)O3 3.282 93
23.5
1 356 1500 215
0.88BT-0.12Bi(Mg0.5Sn0.5)O3 2.25 94
23
0.5 240 1550 216
0.88BT-0.12Bi(Li0.5Nb0.5)O3 2.032 88 19.8 1.2 270 1050 217
0.88BT-0.12Bi(Li1/3Zr2/3)O3 3 93.8 26.15 0.92 285 1500 218
0.9BT-0.1Bi(Li0.5Ta0.5)O3 2.2 89
20
1.6 280 1000 219
0.88BT-0.12Bi(Li1/3Hf2/3)O3 1.65 95.6
16.7
0.4 230 950 116
0.9BT-0.1Bi(Zn0.5Zr0.5)O3 2.46 264 2550 220
0.86BT-0.14Bi(Zn0.5Ti0.5)O3 0.81 94 120 1900 221
0.85BT-0.15Bi(Zn0.5Sn0.5)O3 2.41 91.6 23.2 0.53 230 1100 222
0.9BT-0.1Bi(Ni0.5Sn0.5)O3 2.53 93.9 25.01
0 240 1835 223
0.88BT-0.12Bi(Ni2/3Nb1/3)O3 2.09 95.9 24.01
0 200 1250 224
0.84BT-0.16Bi(Ni2/3Ta1/3)O3 2.63 90 17.4 0.95 375 750 225
0.92BT-0.08(K0.73Bi0.09)NbO3 2.51 86.9
28
3 327 2500 129
0.91BT-0.09BiYbO3 0.71 82.6
17.5
1 93 2500 226
0.7BT-0.3BiScO3 2.3
27
1 225 950 41
0.8BT-0.2BiYO3 0.316 82.7 9.5 1.1 66 1200 227
0.9BT-0.1BiInO3 0.754 89.4 13.5 0.5
135 1267 228
0.8BT-0.2BiNbO4 0.31 93.97 6.0
0 117.2 600 229
0.93BT-0.07YNbO4 0.614 87 10.5 0.71 173 1500 230
0.85BT-0.15CaSnO3 1.57
76
23
3 230 3000 231
0.92(0.65BT-0.35BNT)-0.08SrY0.5Nb0.5O3 1.36 74.3 26.55 2.68 152 1600 232
0.85(0.65BT-0.35BNT)-0.15Bi(Mg2/3Nb1/3)O3 1.6 90.3 21.4 0.81 182 1300 233
0.9(0.65BT-0.35BNT)-0.1Sr(Sc0.5Nb0.5)O3 2.02 90.18
26
2 206 1650 234
0.3(0.65BT-0.35BNT)-0.7ST 1.4 90 17.08 0.44 196 1050 144
0.94Ba0.9Sr0.1Ti0.9Zr0.1O3-0.06BiYb0.9Sc0.1O3 1.24 50
43.5
7 100 2250 235
0.65(Ba0.98Li0.04)Ti0.98O3-0.35(Sr0.7Bi0.2)TiO3 3.54 75.6 53.2 3.1 410 2700 236
0.88(Ba0.8Sr0.2)TiO3-0.12Bi(Zn2/3Nb1/3)O3 1.62 99.8
16.5
0 225 600 119
0.9BT-0.1Bi(Mg2/3Nb1/3)O3 + MnCO3 1.7 90 16.7 0.6 210 1250 237
0.85BT-0.15Bi(Mg0.5Zr0.5)O3 + MnCO3 1.61 94.3 16.81
0.5 230 1063 117

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spark plasma sintering (SPS) to further suppress the reaction
between MgO and Ba0.4Sr0.6TiO3 during the sintering process
and achieved a Wrec of 1.5 J cm3 and a h of 88.5% in
0.95Ba0.4Sr0.6TiO3-0.05MgO ceramic.103 In addition, Pu and Jin
et al. systematically investigated the effect of glass (BaO-TiO2-
SiO2, Bi2O3-B2O3-ZnO, BaO-B2O3-SiO2-Na2CO3-K2CO3, SrO-B2O3-
SiO2) on the energy storage performance of Ba0.4Sr0.6TiO3.199–202
It was found that the glass additives can decrease the sintering
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4.1.4 BT-based relaxor ferroelectric ceramics. For BT-based
relaxor ferroelectrics, the tailoring strategy is to enhance the
relaxation behavior, induce nanodomains or PNRs and opti-
mize the microstructure through A- and B-sites co-doping, as
Fig. 12 shows. Through this method, a slim P–E hysteresis loop
with a low hysteresis loss, a low Pr, a large Pmax and a high Eb can
be expected in BT-based relaxor ferroelectric ceramics,
contributing to both a high Wrec and a high h. The specic

temperature, reduce the grain size and porosity and contribute
to a homogeneous microstructure. With increasing BaO-TiO2-
SiO2 fraction, the grain size gradually decreased, accompanied
by a more homogeneous microstructure, resulting in an
increased Eb (see Fig. 11j). Eventually, a Wrec of 0.6045 J cm3
was achieved in Ba0.4Sr0.6TiO3 ceramic with 5 wt% BaO-TiO2-
SiO2 under 143 kV cm1 due to its moderate 3r and moderate Eb.
Furthermore, Al2O3 and SiO2 were adopted to coat Ba0.4Sr0.6-
TiO3 to form a core–shell structure to improve the Eb, as shown
in Fig. 11f.101,203 Due to the reduced porosity and grain size, the
Eb was enhanced to 493 kV cm1 leading to a high Wrec of 5.09 J
cm3. However, it should be noted that the addition of second
compounds signicantly decreases the 3r and increase the
dielectric loss, especially for glass, as shown in Fig. 11h and
j.103,201 So, the type and amount of the doped compounds are
very important. A proper amount of doping contributes to an
enhanced energy storage performance, while excessive doping
deteriorates the energy storage properties.
energy storage performance of this kind of materials is
summarized in Table 8.
Currently, the most widely studied material system of BT-
based relaxor ferroelectrics is BT-Bi(M)O3, where M represents
one trivalent cation or more cations with an average trivalent
oxidation state. As Bi(M)O3 is incorporated, a phase transition
from tetragonal to pseudocubic is observed at room tempera-
ture and this phase transition usually occurs when the mole
fraction of Bi(M)O3 is between 0.05 and 0.15, depending on the
tolerance factor of Bi(M)O3 compounds, as shown in Fig. 13a.205
In addition, pure BT exhibits an obvious rst-order phase
transition at the temperature of Tm. Aer substitution, this
phase transition temperature shis to a lower temperature and
becomes broad (see Fig. 13b), showing a weakly coupled relaxor
behavior.206 Specically, upon incorporation of a low amount of
Bi(M)O3, the dielectric response starts to deviate from the
Curie–Weiss law at temperatures above Tm, but the frequency
dispersion cannot be observed, as shown in Fig. 13c. When the

Fig. 13 (a) Representative qualitative phase diagram for BaTiO3–Bi(M)O3 systems. (b) 3r as a function of temperature at 1 kHz for (1  x)BaTiO3-
xBi(Zn0.5Ti0.5)O3. 3r and dielectric loss of (c) 0.93BT-0.07Bi(Zn0.5Ti0.5)O3 and (d) 0.89BT-0.11Bi(Zn0.5Ti0.5)O3 as a function of temperature at
various frequencies. (e) The resistivity and activation energies for charge transport of BT-based X7R and Y5V capacitors, as well as PZT-5a, and
0.8BT-0.2Bi(Zn0.5Ti0.5)O3 ceramics as a function of temperature. (f) P–E hysteresis loops of (1  x)BT-xBi(Mg2/3Nb1/3)O3 ceramics measured at
room temperature and 10 Hz. (a) and (e) Reprinted with permission from ref. 205. Copyright 2016 John Wiley and Sons. (b)–(d) Reprinted with
permission from ref. 206. Copyright 2013 John Wiley and Sons. (f) Reprinted with permission from ref. 207. Copyright 2014 John Wiley and Sons.

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concentration of Bi(M)O3 further increases, this solid solution
becomes a relaxor ferroelectric, exhibiting the characteristics of
both the diffuse phase transition and the frequency dispersion
of the 3r, as displayed in Fig. 13d. In this state, the stability of 3r
in response to the temperature and external electric elds is
signicantly enhanced, while maintaining a relatively high 3r
(
1000). Furthermore, the addition of Bi-based compounds can
decrease the sintering temperature and promote the densica-
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on the above discussion, a moderate 3r with excellent stability,
a high Eb and a slim P–E hysteresis loop with a low Pr and
a moderate Pmax can be expected in BT-Bi(M)O3 ceramics
through doping an appropriate amount of Bi(M)O3, demon-
strating great potential in electrical energy storage.
The energy storage performances of BT-Bi(M)O3 ceramics
were initially investigated in 0.7BT-0.3BiScO3 ceramics by Ogi-
hara et al. in 2009.41 Results show that 0.7BT-0.3BiScO3 ceramic
with a thickness of 0.2 mm exhibits a Wrec of 2.3 J cm3 under

tion process, resulting in a low dielectric loss, a dense micro-

structure and a large activation energy in BT-Bi(M)O3 ceramics,
as shown in Fig. 13e, which are in favor of a high Eb.205 In
addition, the incorporation of Bi(M)O3 disturbs the long-range
ordering and promotes the formation of polar nanoregions
(PNRs) due to induced local electric elds, leading to a slim P–E
hysteresis loop (see Fig. 13f). Meanwhile, the hybridization
between Bi 6p and O 2p is expected to improve the Pmax due to
the similar electronic structure between Bi3+ and Pb2+.113 Based
225 kV cm1. Of particular importance is that a large Wrec of 6.1
J cm3 was achieved in this material accompanied with excel-
lent thermal stability by fabricating single dielectric layer
capacitors with a thickness of 15 mm. The excellent energy
storage performance of 0.7BT-0.3BiScO3 ceramics attracts much
attention to BT-Bi(M)O3 ceramics, and later a series of BT-Bi(M)
O3 ceramics were reported for electrical energy storage, as
shown in Table 8. For example, Yuan et al. studied the energy

Fig. 14 Bright field transmission electron microscope micrographs of the (1  x)BT-x Bi(Mg0.5Zr0.5)O3 ceramics for (a) x ¼ 0, (b) x ¼ 0.05, and (c)
x ¼ 0.15. (d) P–E hysteresis loops of (1  x)BT-xBi(Mg0.5Zr0.5)O3 ceramics. (e) Energy storage properties of (1  x)BT-x Bi(Mg0.5Zr0.5)O3 ceramics.
(f) P–E hysteresis loops of 0.87BT-0.13 Bi(Zn2/3(Nb1xTax)1/3)O3 ceramics under 150 kV cm1 with the image of 0.87BT-0.13Bi(Zn2/3(Nb0.85Ta0.15)1/3)O3
bulk ceramics and the corresponding Pmax and Pr values of 0.87BT-0.13Bi(Zn2/3(Nb1xTax)1/3)O3 ceramics at 150 kV cm1. (g) P–E hysteresis loops and
(h) energy storage properties of 0.87BT-0.13Bi(Zn2/3(Nb0.85Ta0.15)1/3)O3-based MLCC at different electric fields. (a)–(e) Reprinted with permission from
ref. 208. Copyright 2018 Elsevier. (f)–(h) Reprinted with permission from ref. 209. Copyright 2019 John Wiley and Sons.

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storage properties of (1  x)BT-xBi(Mg0.5Zr0.5)O3.208 With However, the Eb achieved in 0.87BT-0.13Bi(Zn2/3(Nb0.85Ta0.15)1/3)O3

increasing Bi(Mg0.5Zr0.5)O3 content, the normal ferroelectric
domains in BT are gradually broken accompanied by the
emergence of PNRs, as shown in Fig. 14a–c. Compared with
normal ferroelectric domains, PNRs exhibit low switching
energy barriers and high dynamics, contributing to obtain
a slim P–E hysteresis loop with nearly linear polarization
behavior. Meanwhile, aer substitution, decreased grain size,
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ceramics was still relatively low (218 kV cm1), leading to a low Wrec
of 1.44 J cm3, as shown in Fig. 14f. To further improve the Eb,
a MLCC with a layer thicknesses of 5 mm was fabricated by a tape
casting method. Aer fabricating a MLCC, the Eb of 0.87BT-
0.13Bi(Zn2/3(Nb0.85Ta0.15)1/3)O3 ceramics was signicantly
enhanced from 218 kV cm1 to 1047 kV cm1, nally leading to
an ultrahigh Wrec of 10.12 J cm3 and a high h of 89.4%, as

increased density and enhanced temperature stability were
achieved in this dielectric material. These features lead to
a gradually slim P–E hysteresis loop and an enhanced Eb in
(1  x)BT-xBi(Mg0.5Zr0.5)O3 ceramics, as presented in Fig. 14d.
Finally, a Wrec of 2.9 J cm3 and a h of 86.8% were achieved in
0.85BT-0.15Bi(Mg0.5Zr0.5)O3 ceramics under 280 kV cm1 (see
Fig. 14e). The energy storage performance of this material
maintained good stability in the temperature range from 30  C
to 150  C. In addition, Zhao et al. studied the energy storage
properties of 0.87BT-0.13Bi(Zn2/3(Nb1xTax)1/3)O3 ceramics.209 It
was found that the substitution of Ta for Nb can effectively
decrease the leakage current, contributing to a high Eb.
shown in Fig. 14g and h. Recently, through multiscale optimi-
zation and construction of a core–shell structure, the Wrec of
0.87BT-0.13Bi(Zn2/3(Nb0.85Ta0.15)1/3)O3-based MLCC was further
increased to 18.24 J cm3.118 The improvement of Eb plays an
important for the enhanced Wrec in these materials.
Another drawback of BT-Bi(M)O3 ceramics is their relatively
low Pmax. Apart from increasing the Eb and decreasing the Pr,
the addition of Bi(M)O3 also deteriorates the macroscopic
polarization, limiting the Wrec. To solve this problem, Hu et al.
proposed a strategy of nano-scale polarization mismatch and
reconstruction to achieve a high energy storage performance.210
The schematic diagram of this strategy is shown in Fig. 15a–h.

Fig. 15 (a)–(h) Schematic diagram of the strategy of nano-scale polarization mismatch and reconstruction to achieve a high energy storage
performance. (i) P–E hysteresis loops and (j) I–E hysteresis loops of (1  x)BT-xBi(Mg0.5Ti0.5)O3 ceramics measured at room temperature and
1 Hz. (k) The electric field dependence of Pmax value of (1  x)BT-xBi(Mg0.5Ti0.5)O3 ceramics. (a)–(k) Reprinted with permission from ref. 210.
Copyright 2019 Elsevier.

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Fig. 16 (a) Comparison of h versus Wrec of different BT-based material systems. (b) Publications on different types of BT-based materials for
energy storage. (c) Wrec versus Eb of BT-based ceramics. (d) Influence of different types of M ions on the Wrec of BT-based relaxor ferroelectric
ceramics and the data are from these ref. 37, 208, 213, 215, 217, 219–221, 224 and 225.
For pure BT, the ferroelectricity comes from the displacement of
B site cations, namely, B–O coupling. Aer substitution with
Bi(M)O3, the B–O coupling is disturbed accompanied by the
establishment of A–O coupling because of the ferroelectric
activity of Bi3+ ions. So, large ferroelectric domains, Ti-rich
PNRs and Bi-rich PNRs coexist in BT-Bi(M)O3 ceramics under
a low concentration Bi(M)O3, as shown in Fig. 15b. With
increasing Bi(M)O3, the large ferroelectric domains are
completely interrupted, leading to a low Pr. However, the
establishment of A–O coupling cannot compensate the degen-
eration of macroscopic polarization caused by the interruption
of B–O coupling under a low concentration of Bi(M)O3, resulting
in a moderate Pmax (see Fig. 15g). In this case, either B–O
coupling or A–O coupling can dominate the macroscopic
polarization, namely, a nano-scale polarization mismatch, as
shown in Fig. 15c. With further increasing the concentration of
Bi(M)O3, effective A–O coupling will be established, which can
compensate the decrease of macroscopic polarization caused by
the breaking of B–O coupling, leading to an enhanced Pmax (see
Fig. 15g and h). (1  x)BT-xBi(Mg0.5Ti0.5)O3 ceramics were
selected as an example to verify this strategy. As Fig. 15i–k show,
with increasing concentration of Bi(Mg0.5Ti0.5)O3, the Pmax of
(1  x)BT-xBi(Mg0.5Ti0.5)O3 ceramics rst decreases and then
increases under the same electric eld, which is different from
the polarization behavior in other BT-based ceramics, namely,
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the Pmax decreases linearly with the increase in the secondary
additives. Furthermore, a roll forming process was adopted to
fabricate high-quality bulk ceramics to enhanced the Eb. Even-
tually, both a large DP and a high Eb were achieved in 0.6BT-
0.4Bi(Mg0.5Ti0.5)O3 ceramics, leading to a high Wrec of 4.49 J
cm3 and a h of 93% under 340 kV cm1 with a sample thick-
ness of 0.1 mm.
4.1.5 Summary of BT-based ceramics. BT-based ferroelec-
tric ceramics typically have a high 3r, which contributes to
a large Pmax. However, the high dielectric loss results in a low Eb
and the apparent hysteresis behavior leads to a low h. For BT-
based paraelectric ceramics, a slim P–E hysteresis and a high
Eb can be expected in these ceramics due to their extremely low
dielectric loss, but the absence of dipoles results in a low Pmax
and hence a low Wrec. In contrast, BT-based relaxor ferroelec-
trics exhibit a moderate Pmax, a low Pr and a moderate Eb, which
are more suitable for energy storage applications. As Fig. 16a
shows, BT-based ferroelectric and paraelectric ceramics show
a low Wrec or a low h, while both a high Wrec and a high h are
achieved in BT-based relaxor ferroelectrics. It should be noticed
that the energy storage performance achieved in BT-based
relaxor ferroelectrics exhibits excellent thermal stability due to
the temperature-insensitive 3r in a wide temperature range. Due
to their superior energy storage properties, the research on BT-
based relaxor ferroelectrics attracts substantial attention, as
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Table 9 Summary of energy storage properties of BF-based bulk ceramics

Composition Wrec (J cm3) h (%) Pmax (mC cm2) Pr (mC cm2) Eb (kV cm1) Ref.

0.97(0.65BF-0.35BT)-0.03Nb2O5 0.71 25.2 5.3 90 43

0.61BF-0.33BT-0.06Ba(Mg1/3Nb2/3)O3 1.56 75 38 5.7 125 246
0.61BF-0.33BT-0.06La(Mg0.5Ti0.5)O3 1.66 82 37.5 4.2 130 247
0.54BF-0.34BT-0.12(Sr0.7Bi0.2)TiO3 1.74 74
35
4 150 248
0.6BF-0.34BT-0.06Sr(Al0.5Nb0.5)O3 1.75 81 45.5 8.4 155 249
0.56BF-0.33BT-0.1NN + MnO2 + BaCu(B2O5) 8.12 90
54
2.5 360 250
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0.65BF-0.3BT-0.05Bi(Zn2/3Nb1/3)O3 + Mn2O3 2.1 55.7 36.7 3.8 180 251

0.6BF-0.34BT-0.06Ba(Zn1/3Ta2/3)O3 + MnCO3 2.56
72
47.4
4 160 252
0.61BF-0.33(Ba0.8Sr0.2)TiO3-0.06La(Mg2/3Nb1/3)O3 + MnO2 + BCB 3.38 59 44.1 3.38 230 253
0.75(Bi0.85Nd0.15)FeO3-0.25BT 1.82 41.3 39.8 9.1 170 254
Bi0.83Sm0.17Fe0.95Sc0.05O3 2.21 76 25.2 4.4 230 255
0.67Bi0.9Sm0.1FeO3-0.33BT 2.8 55.8
47.5
9.5 200 256
0.52Bi0.98La0.02FeO3-0.48BT + MnO2 1.22 58 33
7.5 140 257
0.56BF-0.3BT-0.14AN + CuO 2.11 84
28
2.5 195 258

conrmed in Fig. 16b. In addition, the Wrec of BT-based
ceramics increases almost linearly as the Eb improves (see
Fig. 16c). The Eb could therefore be further improved in future
research by an effective strategy to enhance their energy storage
performance. BT-BiMO3 ceramics are the most extensively
studied BT-based relaxor ferroelectrics and the type of M ion
can affect the energy storage performance. As shown in Fig. 16d,
Ta5+ ions are more conducive to a high Wrec in comparison with
Nb5+ ions. This phenomenon can be ascribed to the larger band
gap of Ta2O5 (Eg (Ta2O5) z 4 eV, Eg (Nb2O5) z 3.4 eV), which
contributes to achieving a high Eb in BT-BiMO3 ceramics and
thereby a high Wrec.238,239 In addition, the Wrec in BT-BiMO3

Fig. 17 (a) Phase diagram of (1  x)BF-xBT ceramics based on 3r (T) and DSC measurements. (b) P–E hysteresis loops of (1  x)BF-xBT ceramics at
room temperature. (c) P–E hysteresis loops of (0.66x)BF-0.34BT-xBa(Zn1/3Ta2/3)O3 ceramics. (d) The corresponding Pmax, Pr, and DP of (0.66 
x)BF-0.34BT-xBa(Zn1/3Ta2/3)O3 ceramics as a function of Ba(Zn1/3Ta2/3)O3 concentration. (a) Reprinted with permission from ref. 266. Copyright
2009 John Wiley and Sons. (b) Reprinted with permission from ref. 268. Copyright 2013 Elsevier. (c) and (d) Reproduced from ref. 252 with
permission from The Royal Society of Chemistry.

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ceramics with M of Zr4+ ions is higher than that with M of Ti4+
ions (see Fig. 16d). Compared with Ti4+ ions, Zr4+ ions are more
stable under an external electric eld or a high temperature,
which is in favor of a low leakage current and hence a high Eb.
These results can give some guidance for the development of
high-performance BT-BiMO3 ceramics in future research.
4.2 BiFeO3 (BF)-based ceramics
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However, the large leakage current makes BF ceramics break-
down under a low electric eld, suppressing the presence of
a large spontaneous polarization. The leakage current in BF
ceramics is mainly based on the following two aspects. For
extrinsic factors, the volatilization of Bi3+ and the reduction of
Fe3+ to Fe2+ during high temperature sintering resulted in
secondary phases (e.g., Bi2Fe4O9 and Bi25FeO39) and several
vacancy-related defects.243 For intrinsic factors, the direct band

gap of pure BF ceramics is relatively small (2.67 eV), which

4.2.1 Physical properties. The existence of simultaneous
makes it simple to excite electrons from the valence band to the
ferromagnetism and ferroelectricity at room temperature
conduction band upon an external electric eld.244,245 Table 9
makes BF the most promising multiferroic materials for
summarizes the energy storage performance of BF-based
memories and spintronics applications. At room temperature,
ceramics.
BF exhibits a ferroelectric a phase (rhombohedral, R3c) with
4.2.2 Design strategy. To inhibit leakage current, chemical
a ¼ 3.965 Å and the FeO6 octahedra tilting angle of 11 , which
modications were adopted as an effective strategy for tailoring
undergoes a phase transition to a paraelectric b phase (ortho-
the electrical properties of BF ceramics such as replacing Bi by
rhombic, Pbnm) between 820  C and 830  C.240 The application
rare earth elements (e.g. Sm, Nd, Dy and La) or introducing
of BF for energy storage is mainly based on its large sponta-
other ABO3 compounds (e.g. BaTiO3, SrTiO3, PbTiO3 and Bi0.5-
neous polarization (100 mC cm2) due to the large ionic Bi
K0.5TiO3) to form new solid solutions.259–264 Among them, (1  x)
displacement induced by stereo chemically active 6 s lone
BF-xBT is the most studied solid solution.265 With increasing the
pairs.241 Also, the high Curie temperature (
836  C) of BF makes
concentration of BT, the phase structure of (1  x)BF-xBT
it a good material for high-temperature applications. Xu et al.
ceramics changes from a rhombohedral phase (0.0 # x # 0.33)
predicted that Nd-doped BF materials would have a ultra-high
to a pseudo-cubic phase (0.33 # x # 0.94) and nally to
Wrec of
150 J cm3 through rst-principle calculations.242

Fig. 18 (a) Out-of-plane PFM amplitude and phase images of (0.67  x)BF-0.33BT-xNN ceramics: (a1) x ¼ 0, (b1) x ¼ 0.04, (c1) x ¼ 0.10 and (d1)
x ¼ 0.15. The variation of (b) average grain size (Ga), band gap (Eg); (c) activation energy (Ea) of grain boundary and room-temperature dielectric
loss (tan d) at 1 MHz with changing NN content. (d) P–E hysteresis loops and dP/dE measured, (e) Wrec and h values and (f) pulsed overdamped
discharging WD of x ¼ 0.1 ceramics under different electric fields and at room temperature. (a)–(h) Reprinted with permission from ref. 250.
Copyright 2019 John Wiley and Sons.

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a tetragonal phase (0.94 # x # 1.0), as shown in Fig. 17a.243,266,267
Especially when x ¼ 0.33, a temperature independent mor-
photropic phase boundary is obtained in (1  x)BF-xBT
ceramics, consisting of a polar rhombohedral structure and
a non-polar cubic phase.268 In this state, (1  x)BF-xBT ceramics
exhibit a large 3r with good thermal stability and a high Pmax (see
Fig. 17b), which are more suitable for electrical energy
storage.265,267,268 However, the large Pr of (1  x)BF-xBT ceramics
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Wrec. To solve this problem, advanced sintering methods or
doping sintering aids have been adopted to optimize the
microstructure and then enhance the Eb.253,255,257,258,266 For
instance, a dense microstructure is achieved in Bi0.83Sm0.17-
Fe0.95Sc0.05O3 through hot-press sintering, resulting in a high Eb
of 230 kV cm1 and a Wrec of 2.21 J cm3.255 Also, the Eb of (1  x)
BF-xBT-based ceramics can be signicantly improved through
doping MnO2 due to the increased grain boundary resistivity

results in a low Wrec. Through introducing additive oxides,
doping additional ABO3 compounds or substituting Bi by rare
earth elements, the Pr can be effectively reduced due to the
enhanced relaxation behavior and the emergency of
PNRs.43,249,251,253,269 For example, the Pr value of 0.65BF-0.35BT
was decreased from previous
40 mC cm2 to 5.33 mC cm2
aer incorporating 3 mol% Nb2O5, accompanied by an
improved electrical resistivity.43 Eventually, a Wrec of 0.71 J cm3
was achieved under 90 kV cm1. Similarly, Liu et al. adopted
Ba(Zn1/2Ta2/3)O3 to generate local compositional inhomogeneity
and then constructed local random elds to induce long-range
order to weakly coupled PNRs, generating a large DP value.252 It
was found that the P–E hysteresis loops become slim and
pinched with increasing Ba(Zn1/2Ta2/3)O3 (see Fig. 17c), and the
Pr was decreased from 31.46 mC cm2 to 1.67 mC cm2 when the
concentration of Ba(Zn1/2Ta2/3)O3 increased from 0 to 10%, as
shown in Fig. 17d. Finally, a large DP of 43.41 mC cm2 was
achieved in 0.6BF-0.34BT-0.06Ba(Zn1/3Ta2/3)O3 ceramics under
160 kV cm1, leading to a high Wrec of 2.56 J cm3.
Apart from the large Pr, another drawback of (1  x)BF-xBT-
based ceramics is their relatively low Eb, limiting the increase of
and the reduced concentration of oxygen vacancies.257,270
Recently, Qi et al. used a comprehensive optimization strategy
to improve the energy storage performance of (1  x)BF-xBT-
based ceramics. First, NaNbO3 (NN) was employed to induce
nanoscale domains due to the formed compositional inhomo-
geneity, as shown in Fig. 18a. The nanoscale domains
contribute to a slim P–E hysteresis loop with a nearly linear
response towards polarization and a temperature-insensitive 3r.
Then, they further improved the Eb by optimizing the compo-
sition and adding sintering aids. The incorporation of NN
accompanied with the doped sintering aids (MnO2 and
BaCu(B2O5)) effectively increases the band gap, decreases the
grain size and enhances the resistivity, as shown Fig. 18b and c.
Beneting from the optimization of both intrinsic and extrinsic
breakdown factors, the Eb of (0.67  x)BF-0.33BT-xNN was
increased monotonously from 230 kV cm1 to 420 kV cm1
when the concentration of NN increases from x ¼ 0 to x ¼ 0.15.
Eventually, a slim P–E hysteresis loop with a low Pr, a large Pmax
and a high Eb was achieved in 0.57BF-0.33BT-0.1NN ceramics,
resulting in both a large Wrec of 8.12 J cm3 and a high h of 90%
(see Fig. 18d and e). Meanwhile, the energy storage performance

Fig. 19 (a) Backscattered electron micrographs of polished surfaces of (1  x)BF-0.3BT-xBi(Li0.5Nb0.5)O3 (x ¼ 0.00, 0.13) ceramics. (b) Combined
Z00 and M00 spectroscopic plots at 250  C of (1  x)BF-0.3BT-xBi(Li0.5Nb0.5)O3 (x ¼ 0.00, 0.13) ceramics. (c) P–E hysteresis loops of (1  x)BF-
0.3BT-xBi(Li0.5Nb0.5)O3 ceramics. (d) Backscattered electron cross section micrographs and (e) energy-dispersive X-ray mapping of each
elemental metal distribution of 0.57BF-0.3BT-0.13Bi(Li0.5Nb0.5)O3 MLCCs. (f) Energy storage properties of 0.57BF-0.3BT-0.13Bi(Li0.5Nb0.5)O3
MLCCs under different electric fields. (a)–(f) Reproduced from ref. 273 with permission from The Royal Society of Chemistry.

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Fig. 20 (a) Pmax as a function of Pr for BT, KNN and BF-based ceramics. (b) Wrec as a function of Eb of BF-based ceramics.

of 0.57BF-0.33BT-0.1NN ceramics exhibits excellent thermal materials such as 0.62BF-0.3BT-0.08Nd(Zn0.5Zr0.5)O3, 0.57BF-

stability in the temperature from 50  C to 250  C under 250
kV cm1. The 0.57BF-0.33BT-0.1NN ceramics possess a fast
discharging speed under 200 kV cm1 with a discharging time
of t0.9 z 97 ns (see Fig. 18f).
In contrast, by controlling the electrical homogeneity, Wang
et al. developed a series of high-performance BF-based
0.30BT-0.13Bi(Li0.5Nb0.5)O3 and 0.5BF-0.4SrTiO3-0.03Nb-
0.1Bi(Mg2/3Nb1/3)O3.271–273 As Fig. 19a shows, pure 0.7BF-0.3BT
ceramic exhibits a large grain size of
8 mm. Aer incorpo-
rating Bi(Li0.5Nb0.5)O3, the grain size is signicantly decreased
together with a formation of an obvious core–shell structure due
to the immiscibility of the perovskite end members (see

Fig. 21 Schematic diagram of the tailoring strategy for KNN-based ceramics.

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Fig. 22 (a) SEM images and (b) corresponding grain size distributions of 0.85KNN-0.15ST ceramics. (c) P–E hysteresis loops of 0.85KNN-0.15ST
ceramics at room temperature under different electric fields. (d) SEM image and (e) photograph of transparent 0.8KNN-0.2Sr(Sc0.5Nb0.5)O3
ceramics. (f) P–E hysteresis loops of 0.8KNN-0.2Sr(Sc0.5Nb0.5)O3 ceramics at room temperature under different electric fields. (g) Schematic
diagram of transition liquid phase sintering. (a)–(c) Reproduced from ref. 44 with permission from The Royal Society of Chemistry. (d)–(f)
Reproduced from ref. 280 with permission from The Royal Society of Chemistry. (g) Reproduced from ref. 299 with permission from The Royal
Society of Chemistry.

Fig. 19b). This core–shell structure can increase the electrical
homogeneity. As impedance spectroscopy shows, two electrical
components are observed in the M00 spectra, where the lower
frequency component is the resistance of the shell and the
higher frequency component represents the resistivity of the
core. Wide separation of their maximum frequency for undoped
0.7BF-0.3BT ceramics suggests an electrical inhomogeneity.
With increasing Bi(Li0.5Nb0.5)O3 concentration, the higher
frequency M00 peak gradually decreases and nally disappears
when x $ 0.13 with an enhanced amplitude of the M00 peak,
showing a good electrical homogeneity and a higher resistance.
These properties are conducive to obtaining a high Eb. Also, the
addition of Bi(Li0.5Nb0.5)O3 gradually decreases the Pmax and Pr
due to the enhanced relaxor behavior, contributing to a slim P–E
hysteresis loops (see Fig. 18(c)). As a result, a Wrec of 3.64 J cm3
and a h of 76.8% are obtained in 0.57BF-0.3BT-0.13Bi(Li0.5Nb0.5)
O3 bulk ceramics under 260 kV cm1. To further tap their
potential in electrical energy storage applications, MLCCs were
fabricated to increase the Eb and energy storage performance.
As Fig. 19d and e show, the thickness of a single layer is about

8 mm and Pt was selected as the electrode. Due to the reduced
thickness, the Eb of 0.57BF-0.3BT-0.13Bi(Li0.5Nb0.5)O3 ceramics
was improved to 950 kV cm1, leading to an ultrahigh Wrec of
13.8 J cm3 and a high h of 81%, as shown in Fig. 19f,
demonstrating great potential for practical applications.
4.2.3 Summary of BF-based ceramics. Currently, the
research of this material system is mainly focused on (1  x)BF-
xBT. For these materials, an obvious feature is their high Pmax
(see Fig. 20a), which is benecial to obtain a high Wrec under
a low electric eld. But there are still some problems that need
to be solved. Firstly, the Pr of BF-based ceramics is relatively
large (see Fig. 20a), resulting in a moderate h, which is expected
to be further reduced via composition or fabrication process
optimization. Secondly, the high leakage current results in a low

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Fig. 23 SEM images of (1  x)KNN-xBF ceramics with their grain size distribution and average grain size inserted: (a) x ¼ 0 and (b) x ¼ 0.10. PFM
images in amplitude mode of (1  x)KNN-xBF ceramics with (c) x ¼ 0 and (d) x ¼ 0.10. (e) P–E hysteresis loops of 0.9KNN-0.1BF ceramics under
different electric fields. (f) The Wrec and h of 0.9KNN-0.1BF ceramics as a function of applied electric field. (g) Bending strength, (h) hardness and
(i) compression strength of pure KNN and 0.9KNN-0.1BF ceramics. (a)–(i) Reprinted with permission from ref. 304. Copyright 2019 Elsevier.

Eb. Although the Eb of BF-based ceramics can be enhanced
through composition modication such as introducing MnO2
to suppress dielectric loss or doping BaCu(B2O5) to promote
sintering. However, the Eb of most samples is still below 250
kV cm1, limiting the further improvement of the Wrec (<3.5 J
cm3) (see Fig. 20b). For BF-based ceramics, the enhancement
of Eb is still an effective strategy to achieve a high energy storage
performance. As Fig. 20b shows, a high Wrec of 8.12 J cm3 was
obtained due to the large Eb. In future research,
a comprehensive optimization strategy from chemical compo-
sition (sintering aid, dielectric loss inhibitor), to preparation
process (advanced sintering methods) and to device congura-
tion (thickness and electrode) would be a good choice to
signicantly improve the Eb and then achieve a high Wrec. Some
other material systems also deserve to be studied to develop
high-performance ceramics such as (1  x)BF-xST and (1  x)
BF-xBi0.5K0.5TiO3.

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4.3 (K0.5Na0.5)NbO3 (KNN)-based ceramics decreases the porosity and increases the density, resulting in an
enhanced Eb of 400 kV cm1 with a Wrec of 2.6 J cm3 in 0.8KNN-
4.3.1 Physical properties and design strategy. In the past 20
0.2Sr(Sc0.5Nb0.5)O3-0.5 mol% ZnO ceramics.
years, KNN-based ceramics have received considerable atten-
For dielectric materials, apart from a large Wrec, a high h,
tion due to their excellent piezoelectric performance and envi-
good thermal stability and excellent fatigue resistance, high
ronmental friendliness.274–276 The research mainly focused on
mechanical performance is also required to ensure dielectric
their piezoelectric effect, electro-optic effect and electrocaloric
capacitors work well in severe conditions, such as high
effect, while their energy storage properties were not reported
until 2016.44,274,277–283 Undoped KNN ceramic is not suitable for mechanical pressure and high vibration.300,301 To achieve this,
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electrical energy storage due to its low Eb and high Pr, leading to Yang et al. rst achieved a large DP through the use of
a secondary BF compound. Due to the hybridization between Bi
a low Wrec. As discussed above, the Eb of polycrystalline
6p and O 2p orbitals, the addition of BF improves the polarity of
ceramics is related to many factors, such as porosity, grain size,
the A-site, resulting in a high Pmax. Meanwhile, nanodomains or
impurity phase and band gap. Among them, grain size has been
PNRs were formed in (1  x)KNN-xBF due to the induced local
proven to be an important factor, namely, the Eb increases
electric elds aer doping BF, resulting in a low Pr, as shown in
dramatically when the grain size decreases. Interestingly,
Fig. 23c and d. Also, apart from the Eb, the mechanical perfor-
a distinctive feature of KNN-based ceramics is that the addition
of suitable ions effectively reduces grain size. The effect of mance of polycrystalline ceramics can also be signicantly
doping different ions on the grain growth of KNN ceramics is enhanced by decreasing the grain size, namely, grain-size
strengthening.302,303 It was recognized that the mechanical
summarized in Fig. 21.284–298 From these results, it can be found
failure of polycrystalline ceramics is mostly caused by a large
that the equivalent substitutions usually promote grain growth,
number of dislocation movements. Due to the discontinuity of
while non-equivalent substitutions can inhibit grain growth.
slip planes, the dislocation movements can be prevented by the
These phenomena were ascribed to the generated vacancies for
grain boundaries, generating dislocation blocking at the grain
non-equivalent substitutions, which locate near the grain
boundary. Consequently, an enhanced dislocation blocking can
boundaries and suppress mass transportation, resulting in
small grain size. Based on this feature of KNN-based ceramics, be achieved by decreasing grain size because of the increased
Du et al. rst proposed a strategy of compositional engineering number of grain boundaries, contributing to a superior
mechanical performance. Based on this, a submicron grain size
to drive the grain size to submicron scale to signicantly
was achieved through tailoring the composition and optimizing
enhance the Eb, resulting in a high Wrec, as shown in Fig. 21. It
the preparation process to realize both a high Eb and excellent
should be noted that, while doping oxide slightly promotes the
mechanical performance, as shown in Fig. 23a and b. Eventu-
growth of grains, it can signicantly reduce porosity and
ally, a large Wrec of 2 J cm3 was achieved in 0.9KNN-0.1BF
increase density, which is also in favor of a high Eb.
ceramics under a moderate electric eld of 206 kV cm1 (see
4.3.2 Representative studies. To conrm this strategy, ST
was rst selected to tailor the grain size. Aer incorporation of Fig. 23e and f). Meanwhile, the mechanical parameters of
ST, the grain size was obviously decreased from 2.26 mm of pure hardness, bending strength, elastic modulus and compression
strength were also signicantly enhanced in comparison with
KNN ceramics to 0.35 mm of 0.85KNN-0.15ST ceramics, as
pure KNN ceramics, especially for the hardness, which was
shown in Fig. 22a and b. Beneting from the submicron grain
improved around 5 times. These excellent energy storage
size, an ultrahigh Eb of 400 kV cm1 was achieved in 0.85KNN-
properties and mechanical performance endow 0.9KNN-0.1BF
0.15ST ceramics. As Fig. 22c shows, when the applied electric
ceramics with great potential for capacitors operating in
eld increases, the Wrec of 0.85KNN-0.15ST ceramics gradually
severe conditions.
increases and eventually a large Wrec of 4.03 J cm3 was achieved
under 400 kV cm1.44 This strategy is also proved in the material 4.3.3 Summary of KNN-based ceramics. Table 10 summa-
systems of (1  x)KNN-xBi(Mg2/3Nb1/3)O3 and (1  x)KNN- rizes the energy storage performance of KNN-based bulk
ceramics. A signicant feature of these ceramics is their
xSr(Sc0.5Nb0.5)O3.44,280 For example, a submicron grain size of
submicron grain size, resulting in a high Eb and a high Wrec.
0.5 mm was achieved in 0.8KNN-0.2Sr(Sc0.5Nb0.5)O3 ceramics
Fig. 24a shows a comparison of the grain size among KNN-
(see Fig. 22d).280 The rened grain size not only contributes to
based ceramics and other energy storage materials systems.
a high Eb (300 kV cm1) but also results in a good transparency,
The grain size obtained in KNN-based ceramics is obviously
as presented in Fig. 22e. Eventually, both a large Wrec of 2.48 J
smaller than that of other material systems. This characteristic
cm3 and a high transparency of 60% at 700 nm were realized in
0.8KNN-0.2Sr(Sc0.5Nb0.5)O3 ceramics (see Fig. 22f), demon- not only gives them good transparent properties and excellent
strating great potential in multifunctional optoelectronic mechanical performance, but also makes KNN-based ceramics
are highly promising in MLCC. The submicron grain size means
applications. To further improve the Eb of 0.8KNN-0.2Sr(Sc0.5-
that there are several grains rather than a single grain sepa-
Nb0.5)O3 ceramics, a liquid phase sintering method was
rating the electrodes even when the single layer thickness of
employed and ZnO was selected as the sintering aid. Fig. 22g
MLCC is very low, which can remove the possibility of short
shows the schematic diagram of the transition liquid phase
circuit conduction pathways and then preserve a high Eb.
sintering method. During the sintering process, the emergency
Furthermore, for most KNN-based ceramics, their Wrec and Eb
of a liquid phase wets the grains and then promotes the
densication process. It was found that the addition of ZnO have an approximately linear relationship, as shown in Fig. 24b,
while there is a deviating data point, namely, 0.95KNN-

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0.05Ba(Zn1/3Nb2/3)O3. Due to the ultrahigh Pmax (74 mC cm2),
a high Wrec of 4.87 J cm3 was obtained under a moderate
electric eld (220 kV cm1). More research is required to reveal
the underlying mechanism for the ultrahigh Pmax, and conrm
whether Ba-based materials can also be used to improve the
Pmax. Also, there are some problems that need to be solved for
KNN-based ceramics. Firstly, the growth mechanism of
submicron grains is not fully understood and more experiments
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4.4.2 Design strategy of the rst-type MPB. The material
systems of (1  x)BNT-xBT, (1  x)BNT-xKNN and (1  x)BNT-
x(Bi0.5K0.5)TiO3 exhibit a rhombohedral and tetragonal phases
boundary at certain concentration and temperature. As an
example, for the actively studied (1  x)BNT-xBT ceramics,
a morphotropic phase boundary can be achieved at approxi-
mately 6–8 mol% BT, which separates the rhombohedral BNT-
rich side and the tetragonal BT-rich side.330–332 Although the

are required to reveal the grain growth process. Secondly, the
sintering temperature window of KNN-based ceramics is rela-
tively narrow, and usually less than 5  C, which needs to be
further broadened. Thirdly, the dielectric loss of KNN-based is
signicantly enhanced under a high electric eld, leading to
a low h. So, an effective strategy to suppress the dielectric loss
under high electric elds is also highly expected. At last, KNN-
based lms, MLCC and composites should also be explored in
future research.
4.4 (Bi0.5Na0.5)TiO3 (BNT)-based ceramics
4.4.1 Physical properties. BNT, as another representative
ferroelectric ceramic, was rst discovered by Smolensky et al. in
1961.325 Aer that, enormous efforts were carried out to improve
its piezoelectric properties, while its energy storage perfor-
mance was not studied until 2011 by Gao et al.42 With increasing
temperature, BNT undergoes a series of phase transitions: FE
phase (rhombohedral, R3c) / AFE phase (tetragonal, P4bm and
rhombohedral, R3c) / paraelectric phase (tetragonal, P4bm) /
paraelectric phase (cubic, Pm3m).326 Pure BNT ceramic is not
suitable for electrical energy storage due to its strong ferro-
electricity (coercive eld (Ec), Ec ¼ 73 kV cm1, Pr ¼ 38 mC cm2),
high conductivity and large dielectric loss.327–329 The high phase-
transition (FE-AFE) temperature (
200  C) hinders the emer-
gence of double P–E hysteresis loops at room temperature. To
improve its energy storage performance, composition modi-
cation was adopted to tailor the P–E hysteresis loops of BNT
ceramics by constructing morphotropic phase boundary (MPB).
According to the difference of the MPB, there are mainly two
design strategies for BNT ceramics.
Eb and Pmax values can be enhanced at the MPB in comparison
with pure BNT, the P–E hysteresis loop of 0.94BNT-0.06BT
ceramic still shows a square shape, resulting in a low Wrec
and a low h.327,330,333,334 In addition, the phase transition
temperature (Td) from the FE phase to the AFE phase at MPB is
still relatively high (>100  C), depending on the composition of
BT, which makes it difficult to obtain a double P–E hysteresis
loop at room temperature.335–337 To improve the energy storage
performance, various compounds were introduced into (1  x)
BNT-xBT ceramics to form a ternary system such as KNN, KN,
ST, NN, Ba(Zr0.3Ti0.7)O3, Bi(Zn2/3Nb1/3)O3, (Sr0.7Bi0.2)TiO3,
Ba(Zr0.3Ti0.7)O3 and Bi(Mg0.5Ti0.5)O3.42,324,338–345 The design
strategy of these solid solutions is shown in Fig. 25, namely,
constructing room-temperature FE-AFE phase boundaries to
obtain double P–E hysteresis loops at room temperature.
Table 11 summarizes the energy storage properties of BNT-
based ceramics with rst-type MPB. The rst work was carried
out by Gao et al. They adopted KNN to stabilize the AFE phase of
(1  x)BNT-xBT ceramics.42 Aer incorporating KNN, the FE-
AFE transition becomes rather diffuse and the AFE feature of
four current peaks appears above 50  C, as shown in Fig. 26a
and b. Due to the stable AFE phase, a Wrec of 0.59 J cm3 was
maintained from 100 to 150  C under 56 kV cm1 (see Fig. 26c).
Apart from incorporating a third compound, the high-
temperature AFE phase in (1  x)BNT-xBT ceramic can also
be tailored to room temperature through modulating the Bi/Na
ratio. A metastable AFE phase was obtained at room tempera-
ture when the ratio of Bi/Na is larger than 1. Furthermore, with
the ratio of Bi/Na increasing, the depolarization temperature Td
shied to lower temperatures, leading to an enhanced stability

Table 10 Summary of energy storage properties of KNN-based bulk ceramics

Composition Wrec (J cm3) h (%) Pmax (mC cm2) Pr (mC cm2) Eb (kV cm1) G (nm) Ref.

0.8KNN-0.2Sr(Sc0.5Nb0.5)O3 2.48 81.4 16.4 2.0 295 500 280

0.9KNN-0.1Bi(Mg2/3Nb1/3)O3 4.08 62.5 41 8 300 310 305
0.85KNN-0.15Bi(Mg0.5Ti0.5)O3 2.25 84 28.6
4 275 230 306
0.95KNN-0.05Ba(Zn1/3Nb2/3)O3 4.87 53.3 74
20 220 75 307
0.85KNN-0.15ST 4.03 53 33.3 7.5 400 350 44
0.9KNN-0.1BF 2 60.5 29.4 5.7 206 150 304
0.985KNN-0.015ErBiO3 1.85 69
28.5
4.5 200 120 308
0.94KNN-0.06Sr(Zn1/3Nb2/3)O3 1.5 50 28.6 5.8 180 136 309
0.85KNN-0.15Bi(Zn0.5Zr0.5)O3 3.5 86.8
33
6.5 326 510 310
0.925KNN-0.075Bi(Zn2/3(Ta0.5Nb0.5)1/3)O3 4.02 87.4 37.3
3 307 200 311
(K0.48Na0.52)0.88Bi0.04NbO3 1.04
15.5
2 189 750 312
K0.14Bi0.12Na0.5NbO3 2.89 80 30
3 308 - 313
0.8KNN-0.2Sr(Sc0.5Nb0.5)O3 + ZnO 2.6 73.2 13.1 1.4 400 450 299
0.9KNN-0.1Bi(Mg2/3Nb1/3)O3 + CuO 4.02 57.3 32
6 400 490 314
((Na0.5K0.5)0.91Li0.03)(Nb0.88Sb0.06)O3-0.06Bi(Zn0.5Zr0.5)O3 + La2O3 4.85 88.2 31.5
2 480 175 315

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Fig. 24 (a) Comparison of grain size among KNN-based ceramics and other lead-based and lead-free energy storage materials systems (PLZST:
Pb0.97La0.02(Zr0.56Sn0.35Ti0.09)O3, PLLN: La0.03Pb0.965(Lu0.5Nb0.5)O3, PLSZS: Pb0.94La0.02Sr0.04(Zr0.9Sn0.1)0.995, PBLZST: (Pb0.87Ba0.1La0.02)(Zr0.68Sn0.24-
Ti0.08)O3, BNT-ST: 0.7BNT-0.3ST, BDF-BT: 0.75(Bi0.85Nd0.15)FeO3-0.25BT, BSF-BT: 0.67(Bi0.9Sm0.1)FeO3-0.33BT, NN-CZ: 0.96NN-0.04CaZrO3,
BT-BZZ: 0.9BT-0.1Bi(Zn0.5Zr0.5)O3, CZT: CaZr0.5Ti0.5O3, ASNT: (Sm0.02Ag0.94)(Nb0.9Ta0.1)O3, BF-BT-LMT: 0.61BF-0.33BT-0.06La(Mg0.5Ti0.5)O3, ANT:
AgNb0.45Ta0.55O3, NN-BNH: 0.86NN-0.14(Bi0.5Na0.5)HfO3, BNT-BT-NN: 0.9(0.92BNT-0.08BT)-0.1NN, BT-BLN: 0.88BT-0.12Bi(Li0.5Nb0.5)O3, KNN-ST:
0.85KNN-0.15ST, KNN–BF: 0.9KNN-0.1BF) and the date are from these ref. 126, 156, 217, 220, 247, 254, 256, 316–324. (b) Wrec as a function of Eb of
KNN-based ceramics and the data are from Table 10.

Fig. 25 Schematic diagram of the tailoring strategy of (1  x)BNT-xBT based ceramics with a rhombohedral and tetragonal phases boundary.

of the AFE phase. Eventually, a high Wrec of 1.76 J cm3 was
achieved in 0.94Bi0.55Na0.45TiO3-0.06BaTiO3 ceramics under 75
kV cm1.333 However, for most of the chemically modied (1 
x)BNT-xBT ceramics, the observed P–E hysteresis loops are in
a slim or at shape at room temperature in spite of the
decreased depolarization temperature. This may be caused by
two reasons. The rst one is that the introduced third
compound disturbs the AFE phase and promotes a relaxor
ferroelectric. Another reason is that the FE-AFE phase transition
requires a very high electric eld due to the generated random
electric eld via incorporating the third compound, and the
sample has broken down before reaching this value. For
example, a slim P–E hysteresis loop with weak hysteresis
nonlinearity was observed in (Sr0.7Bi0.2)TiO3 modied (1  x)
BNT-xBT ceramics by Li et al.339. This was ascribed to the formed
ergodic relaxor ferroelectric with strong relaxation behavior and
PNRs, as shown in Fig. 26d and e. As a result, a Wrec of 0.5 J cm3
and a h of 90% were obtained in 0.62BNT-0.06BT-0.32(Sr0.7Bi0.2)
TiO3 within the temperature from 25 to 140  C (see Fig. 26f).
Meanwhile, the ceramic exhibits a high power density of 18.2
MW cm3 and a large current density of 606 A cm2, showing
great potential in pulsed power systems.
4.4.3 Design strategy of the second-type MPB. Different
from (1  x)BNT-xBT, the MPB in (1  x)BNT-xST ceramics
occurs between rhombohedral and pseudocubic phases.369,370
Within a certain temperature or composition range, a low-
temperature dielectric anomaly can be observed, which was
attributed to the FE-AFE phase transition in the earlier

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Table 11 Summary of energy storage properties of BNT-based ceramics with first-type MPB

Composition Wrec (J cm3) h (%) Pmax (mC cm2) Pr (mC cm2) Eb (kV cm1) 3r Ref.

0.89BNT-0.06BT-0.05KNN 0.59
27
2 56 2000 42

0.95(0.94BNT-0.06BT)-0.05KNN 0.524
24
5 60 5350 338
0.95(0.93BNT-0.07BT)-0.05KN 1.72
43
9 168 1550 346
0.7(0.94NBT-0.06BT)-0.3ST 0.98 82
33.8
3 90 2700 342
0.6(0.935BNT-0.065BT)-0.4Ba(Zr0.3Ti0.7)O3 1.9 86 1.02 23.1 210 1100 347
0.62BNT-0.06BT-0.32(Sr0.7Bi0.2)TiO3 0.5 90 19
0.5 60 2400 339
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0.825BNT-0.05BT-0.125Bi(Zn2/3Nb1/3)O3 2.83 67
41
6 180 1200 348

0.8(0.92BNT-0.08BT)-0.2Na0.73Bi0.09NbO3 1.36 73.9
27
3.5 136 1400 343
0.9(0.92BNT-0.08BT)-0.1Bi(Mg0.5Ti0.5)O3 2 88
43
3 135 1500 349
0.852BNT-0.028BT-0.12(K0.5Bi0.5)TiO3 0.83 88 75 350
0.4BNT-0.225BT-0.375BF 1.37 75.6
43
3 80 351
{(Bi0.5Na0.5)0.94Ba0.06}0.95La0.05TiO3 1.66
44
4.5 105 352
{(Bi0.5Na0.5)0.94Ba0.06}La0.98Zr0.02TiO3 1.58 37.5
3 83.4 4000 341
Na0.46Bi0.46Ba0.05La0.02Zr0.03Ti0.94Sn0.03O3 1.58 71.7
35.5
3 110 1100 353
(Ba0.06Bi0.47Na0.47)0.98La0.02Ti0.96Zr0.04O3 1.55 72.6
33
3.5 136 354
{(Bi0.5Na0.4K0.1)0.94Ba0.06}0.98La0.02Ti0.975Ta0.025O3 1.56 88.5
37
2.5 95 2000 355
(Bi0.5Na0.5)0.94Ba0.06Ti0.96(Al0.5Nb0.5)0.04O3 0.7 70.4 40.6 7.6 70 1800 345
(Bi0.5Na0.5)0.94Ba0.06Ti0.965(Mg1/3Nb2/3)0.035O3 0.8 65
31
3 70 1750 356
{(Bi0.93La0.07)0.5Na0.5}0.94Ba0.06(Ti0.975Nb0.02)O3 1.83 70 41.82 3.89 135 357
0.9{(Bi0.5Na0.5)0.94Ba0.06}0.98La0.02TiO3-0.1KNb0.6Ta0.4O3 2.1 92.9
31
1 170 2250 358
0.94(Bi0.5Na0.5)(Y0.5Ta0.5)0.03Ti0.97O3-0.06BT 1.215 68.7
34
3 98 359
0.92(Na0.5Bi0.49Nd0.01TiO3)-0.08BT 1.53 93
30
1 73 1400 360
0.95(Bi0.51Na0.47)0.94Ba0.06TiO3-0.05Sm1/3TaO3 1.59 84.2 31.4
0 125 1500 361
0.85(Bi0.5Na0.5)0.94Ba0.06TiO3-0.15BaSnO3 1.2 86.7
26 0.4 115 2000 362
0.95{(Na0.5Bi0.5)0.95Ba0.05}0.98La0.02TiO3-0.05KNN 1.1 80
31
2 90 1800 363
0.9(0.94BNT-0.06BT)-0.1NN + ZnO 1.27 67
41
5 100 3218 364
0.82(0.94BNT-0.06BT)-0.18KNN + ZnO 1.03 72.7
19
2 140 1400 365
0.55 (0.94BNT-0.06BT)-0.45ST + MnCO3 2.98 73.1
20
5 280 1150 366
0.84BNT-0.16KNN 1
34
4 100 367
0.8BNT-0.2(Bi0.5K0.5)(Hf0.03Ti0.97)O3 0.51
47
30
5 60 1400 368

Fig. 26 Switching current curves of 0.89BNT-0.06BT-0.05KNN ceramics under temperatures of (a) 20  C and (b) 50  C. (c) P–E hysteresis loops
of 0.89BNT-0.06BT-0.05KNN ceramics under 110  C. The insert shows the Wrec of 0.89BNT-0.06BT-0.05KNN ceramics under different electric
fields. (d) 3r of 0.62BNT-0.06BT-0.32(Sr0.7Bi0.2)TiO3 ceramic upon heating and cooling and the inset shows the ln(1/3  1/3m) versus ln(T  Tm) at 1
kHz over 270–400  C for the ceramic. (e) PFM image of 0.62BNT-0.06BT-0.32(Sr0.7Bi0.2)TiO3 ceramic. (f) P–E hysteresis loop of 0.62BNT-
0.06BT-0.32(Sr0.7Bi0.2)TiO3 ceramic measured at 1 Hz over 25–160  C (a)–(c) Reprinted with permission from ref. 42. Copyright 2011 John Wiley
and Sons. (d)–(f) Reprinted with permission from ref. 339. Copyright 2017 Elsevier.

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Fig. 27 (a) Schematic diagram of the design strategy of (1  x)BNT-xST ceramics with a rhombohedral and pseudocubic phases boundary.

Table 12 Summary of energy storage properties of BNT-based ceramics with second-type MPB

Composition Wrec (J cm3) h (%) Pmax (mC cm-2) Pr (mC cm2) Eb (kV cm1) 3r Ref.

0.95(0.8BNT-0.2ST)-0.05NN 0.74 55
32
4.5 70 1750 379

0.8(0.95BNT-0.05SrZrO3)-0.2NN 3.14 79
25
3 230 1170 380
0.9(0.75BNT-0.25ST)-0.1Ag(Nb0.85Ta0.15)O3 3.6 80
33
3 290 1691 381
0.99(0.72BNT-0.28ST)-0.01BiAlO3 1.75 71
32
5 120 377
0.95(0.76BNT-0.24ST)-0.05AN 2.03 61.8
50.5
7 120 1500 378
0.96(0.65BNT-0.35Bi0.1Sr0.85TiO3)-0.04NN 3.08 81.4 50.46
4 220 2750 382
0.85(0.65BNT-0.35Bi0.1Sr0.85TiO3)-0.15KN 1.32 82.5 34 0.27 95 2500 383
0.85(0.7BNT-0.3Bi0.1Sr0.85TiO3)-0.15KN 3.72 90.7
37.5
2 290 3000 384
0.65BNT-0.3Bi0.2Sr0.7TiO3-0.05LaTi0.5Mg0.5O3 1.32 75 32.1 1.1 100 1740 385
0.94(0.65BNT-0.35Bi0.1Sr0.85TiO3)-0.06KNN 2.65 84.6
38
2 180 3000 386
0.8(0.775BNT-0.225BaSnO3)-0.2BaZrO3 2.08 88 20
1 245 630 387
(Na0.5Bi0.5)0.8Ba0.2Ti0.8Sn0.2O3 2.35 71 35.8 5 195 2000 388
{Bi0.5((Na0.8K0.2)0.9Li0.1)0.5}0.96Sr0.04(Ti0.975Ta0.025)O3 2.42 64.3 47.5
5 143 1750 389
0.9Bi0.48La0.02Na0.48Li0.02Ti0.98Zr0.02O3-0.1Na0.73Bi0.09NbO3 2.04 54 38 7 178 1000 390
0.94Bi0.5(Na0.78K0.22)0.5Ti0.96 (Al0.5Nb0.5)0.04O3-0.06BaZrO3 1.32 76.6
38
3.5 95 1400 391
0.9(Na0.5Bi0.5)0.7Sr0.3TiO3-0.1Bi(Ni0.5Sn0.5)O3 4.18 83.6
46
3 270 1250 376
0.7(Na0.5Bi0.5)0.7Sr0.3TiO3-0.3Sr(Ti0.85Zr0.15)O3 3.13 91.1
35
2 262 375
0.85(Na0.5Bi0.5)0.7Sr0.3TiO3-0.15Bi(Mg2/3Nb1/3)O3 3.45 88
37
2 250 1200 17
(Bi0.5Na0.6)0.6Sr0.4Ti0.98(Fe0.5Nb0.5)0.02O3 3.36 81
56
6 170 3000 392
0.96Bi0.5Na0.84K0.16Ti0.97Nb0.03O3-0.04SrTiO3 1.0
70 45 2 60 1400 393
0.6Bi0.51Na0.47TiO3-0.4Ba(Zr0.3Ti0.7)O3 3.1 91
29
1.5 280 1140 394
0.7NBT-0.3ST 0.65 73.6
37
6 65 1800 323
0.75Bi0.58Na0.42TiO3-0.25ST 5.63 94
40.5
2 535 1600 374
0.75BNT-0.25BaSnO3 1.91 86.4 24.6
2 190 1605 395
0.75BNT-0.25BaZrO3 1.56 80.6 27.5 2.5 137 4800 396
0.85BNT-0.15BaHfO3 2.1 66.1 34 5 175 1850 397
0.9BNT-0.1LiTaO3 3.1 74.2
28
3 200 1060 398
(Na0.25Bi0.25Sr0.5)(Ti0.8Sn0.2)O3 3.4 90
27
1.5 310 720 123
0.55BNT-0.45Sr0.7La0.2TiO3 4.14 92.2
37
2.5 315 1550 399
0.5BNT-0.5(Ba0.85Ca0.15)(Zr0.1Ti0.9)O3 0.95 69
30
3.5 110 2100 400
0.775BNT-0.225BaSnO3 + MgO 2.13 67.8
30
4 215 550 401
0.95(0.76BNT-0.24ST)-0.05AN + SiO2 3.22
37
8.5 316 750 402

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Fig. 28 (a) Temperature dependency of 3r and dielectric loss of 0.75Bi(0.5+x)Na(0.5x)TiO3-0.25ST ceramics. (b) Plot of ln(T  Tm) versus ln(1/30  1/
30 m) and (c) P–E hysteresis loops for 0.75Bi0.58Na0.42TiO3-0.25ST ceramic. (d) Temperature dependency of 3r and dielectric loss, (e) average grain
size and Eb values and (f) P–E hysteresis loops of (1  x)(0.7BNT-0.3ST)-xSr(Ti0.85Zr0.15)O3 ceramics. (g) Schematic diagram of mitigating
polarization saturation to achieve a high energy storage performance. (h) P–E hysteresis loops of (Na0.25Bi0.25Sr0.5)(Ti1xSnx)O3 ceramics. (i)
Discharge properties of (Na0.25Bi0.25Sr0.5)(Ti0.8Sn0.2)O3 ceramic. (a)–(c) Reprinted with permission from ref. 374. Copyright 2020 Elsevier. (d)–(f)
Reprinted with permission from ref. 375. Copyright 2019 Elsevier. (g)–(i) Reproduced from ref. 123 with permission from The Royal Society of
Chemistry.

research.371 This conclusion is based on the appearance of
double P–E hysteresis loops at high temperature. However,
recent studies indicated that the low-temperature dielectric
anomaly is caused by the ferroelectric to relaxor ferroelectric
phase transition.370,372,373 He et al. presented the phase diagram
of poled (1  x)BNT-xST ceramics.370 With increasing ST
concentration, the phase transition temperature (Ts) of ferro-
electric to relaxor ferroelectric decreases and the P–E hysteresis
loops become slim with decreased Pr and Ec. However, the Pr
and Ec of (1  x)BNT-xST ceramics are still relatively large,
leading to a low Wrec of 0.65 J cm3 at 65 kV cm1 in 0.7BNT-
0.3ST ceramics.323 At present, the tailoring strategy for (1  x)
BNT-xST ceramics is to construct a room temperature ergodic
relaxor ferroelectric phase through composition modication or
introducing defects, causing a slim P–E hysteresis loops with
a large Pmax and a small Pr, as shown in Fig. 27.
Table 12 shows the energy storage performance of BNT-
based ceramics with second-type MPB. For instance, A-site
defect engineering of Bi-excess and Na-deciency was adopted
by Yan et al. to tailor the energy storage performance of (1  x)
BNT-xST ceramics.374 As Fig. 28a and b show, as the concen-
tration of Bi increases, the Ts gradually shis to low tempera-
tures, leading to the change from a nonergodic relaxor state to
a ergodic relaxor state together with an enhanced relaxation
behavior. Beneting from this, a slim P–E hysteresis loop was
achieved in 0.75Bi0.58Na0.42TiO3-0.25ST ceramics. For electrical
energy storage, another important factor is the Eb. For BNT-
based ceramics, oxygen vacancies are usually formed during
the high temperature sintering process because of the volatili-
zation of Bi and Na, especially for Bi, which will inevitably
increase the ion conductivity and then deteriorate the energy
storage performance. The A-site defect engineering of Bi-excess
and Na-deciency can reduce the generation of oxygen

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Table 13 Summary of energy storage properties of BNT-based relaxor-antiferroelectric ceramics

Composition Wrec (J cm3) h (%) Pmax (mC cm2) Pr (mC cm2) Eb (kV cm1) 3r Ref.

0.78BNT-0.22NN 7.02 85
47
2.5 390 1500 403

0.84BNT-0.16KN 5.2 88
38
1 320 1600 406
0.8BNT-0.2NaTaO3 4.21 77.8
30
2.5 380 800 407
0.85BNT-0.15Ag0.91Sm0.03NbO3 2.1 83
28
2.5 170 1300 408
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vacancies. Furthermore, a tape-casting method was adopted to
prepare high-quality ceramics with a thin thickness of
0.04
mm. Finally, the slim P–E hysteresis loop together with a high
Eb of 535 kV cm1 resulted in a large Wrec of 5.63 J cm3 and a h
of 94% in 0.75Bi0.58Na0.42TiO3-0.25ST ceramics. The second
method is to introduce another compound into BNT to induce
the ergodic relaxor state and enhance the relaxation behavior,
such as Sr(Ti0.85Zr0.15)O3, Bi(Mg2/3Nb1/3)O3, Bi(Ni0.5Sn0.5)O3,
BiAlO3, AN, NN etc.17,375–379 For example, Li et al. adopted
Sr(Ti0.85Zr0.15)O3 to modulate the energy storage performance of
0.7BNT-0.3ST ceramics. As Fig. 28d shows, the addition of
Sr(Ti0.85Zr0.15)O3 can signicantly decrease Ts and induce
a relaxor ferroelectric phase at room temperature. Also, the
grain size of (1  x)(0.7BNT-0.3ST)-xSr(Ti0.85Zr0.15)O3 ceramics
was rened from 3.37 mm for x ¼ 0 to 1.48 mm for x ¼ 0.4,
leading to an enhanced Eb from 180 kV cm1 to 280 kV cm1, as

Fig. 29 (a) Temperature dependency of 3r and (b) the phase diagram for (1  x)BNT-xNN ceramics. (c) SAED patterns and the HR-TEM images of
lattice fringes along (111)C and (001)C. (d) P–E hysteresis loops of (1  x)BNT-xNN ceramics under different electric fields. (e) Temperature and (f)
frequency dependent P–E hysteresis loops of 0.78BNT-0.22BT ceramic under an electric field of 250 kV cm1. The room temperature P–E
hysteresis loops of 0.94(Na0.82K0.18)1/2Bi1/2TiO3-0.06FeNbO4/0.96NN-0.04CaZrO3 ceramics with a mass ratios of (g) 100/0, (h) 70/30 and (i) 1/
100 under 80 kV cm1. (a)–(f) Reproduced from ref. 403 with permission from The Royal Society of Chemistry. (g)–(i) Reproduced from ref. 404
with permission from The Royal Society of Chemistry.

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shown in Fig. 28e. Beneting from these properties, the P–E
hysteresis loop gradually becomes slim with an decreased Pr
(see Fig. 28f) and hence a high Wrec of 3.13 J cm3 with a h of
91.14% was realized in 0.7(0.7BNT-0.3ST)-0.3Sr(Ti0.85Zr0.15)O3
ceramic under 262 kV cm1. For (1  x)BNT-xST ceramics,
although an ergodic relaxor state can be constructed at around
room temperature through composition modication, the
polarization of these relaxor ferroelectrics tends to saturate at
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properties, a phase diagram was presented in Fig. 29b. As the
content of NN increases, (1  x)BNT-xNN ceramics undergo
a transition from a nonergodic relaxor ferroelectric state to
a ergodic relaxor ferroelectric state and nally to a AFE state. A
stable room-temperature AFE phase can therefore be achieved
within the range of 0.2 # x # 0.4. The AFE P4bm phase has also
been veried by high resolution transmission electron micros-
copy, as shown in Fig. 29c. In addition, apart from stabilizing

a low electric eld because of the large permittivity tunability,
limiting the further improving of Wrec under high electric elds.
To mitigate the polarization saturation, Sn4+ ions were intro-
duced to partially substitute Ti4+ ions.123 Due to the generated
local strain/stress and the distorted oxygen octahedral, the
polarization saturation trend of (Na0.25Bi0.25Sr0.5)(Ti1xSnx)O3
ceramics becomes weak with increasing Sn4+ concentration, as
shown in Fig. 28h. As a result, both a large Wrec of 3.4 J cm3 and
a h of 90% were obtained in (Na0.25Bi0.25Sr0.5)(Ti0.8Sn0.2)O3
under 310 kV cm1. Also, this ceramic exhibits a fast discharge
speed of 0.63 ms with a load resistor of 2 kU (see Fig. 28i).
4.4.4 BNT-based relaxor-antiferroelectric ceramics. In
order to boost the energy storage performance of BNT-based
ceramics, apart from constructing MPB and then doping
other compounds to optimize the P–E hysteresis loops, a further
technique is to directly induce the AFE phase through compo-
sition modication or preparing relaxor/antiferroelectric
composite ceramics. Table 13 shows a series of BNT-based
relaxor-antiferroelectric ceramics produced by Zuo's group.
The high-temperature AFE phase of BNT ceramics, for example,
was lowered to room temperature by adding NN.403 As shown in
Fig. 29a, the depolarization temperature decreases monoto-
nously with rising NN concentration and falls below room
temperature when x $ 0.2. According to the dielectric
the AFE phase, large random elds are created in ceramics aer
NN has been incorporated, leading to an ultrahigh driving eld
for the AFE-FE phase transition. In this case, a linear-like
dielectric response is observed under a low electric eld due
to the invalidity of the dipoles and double-like P–E hysteresis
loops can only be achieved, if the applied electric eld above the
driving eld is used to trigger the antiparallel spontaneous
polarization vectors. This material system was also studied by
Xu et al.324 However, only linear-like P–E hysteresis loops were
observed because the sample had broken down before reaching
the driving eld due to the low Eb. In view of this, BaCu(B2O5)
and H3BO3 were adopted by Qi et al. as sintering aids to opti-
mize the sintering process. A dense and uniform microstructure
with small grain size was realized in 0.78BNT-0.22NN ceramics,
resulting in an ultrahigh Eb of 390 kV cm1. As a result, the
stable AFE phase, high Eb and the strong relaxation behavior
result in a linear-like double P–E hysteretic loop, as shown in
Fig. 29d. A record Wrec of 7.02 J cm3 as well as a high h of 85%
were achieved in 0.78BNT-0.22NN ceramics under 390 kV cm1.
Meanwhile, the energy storage performance of (1  x)BNT-xNN
ceramics exhibits excellent stability with a wide temperature
and frequency range under 250 kV cm1 (see Fig. 29e and f). It
should be noticed that this ultrahigh driving eld is a major
challenge for most materials, making it impossible to induce

Fig. 30 SEM micrographs of (a) 0.475BNT-0.525Ba0.85Ca0.15Ti0.9Zr0.1O3 ceramics and (b) 0.475BNT-0.525Ba0.85Ca0.15Ti0.9Zr0.1O3-0.5 wt% MgO
ceramics. SEM micrographs of (c) 0.95(0.76BNT-0.24ST)-0.05AN ceramics and (d) 0.95(0.76BNT-0.24ST)-0.05AN + SiO2 ceramics. The grain
size distribution of (e) 0.95(0.76BNT-0.24ST)-0.05AN and (f) 0.95(0.76BNT-0.24ST)-0.05AN + SiO2 ceramics. (g) Schematic diagram of the
prepared (Bi0.5(Na0.8K0.2)0.5)0.96Sr0.04Ti0.99Ta0.01O3/0.7BNT-0.3SrNb0.5Al0.5O3 (BNKSTT/BNT-SNA) ceramics with sandwich structures. (h)
Photograph of the prepared samples. SEM images of the (i) BNT-SNA, (j) BNKSTT layer and (k) the cross-section of the sandwich structures. (a)
and (b) Reprinted with the permission from ref. 409. Copyright 2016 Elsevier. (c)–(f) Reprinted with the permission from ref. 402. Copyright 2019
Elsevier. (g)–(k) Reproduced from ref. 413 with permission from The Royal Society of Chemistry.

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the double P–E hysteresis loop despite of the stable AFE phase.
Recently, Fan et al. suggested another strategy to achieve
a double P–E hysteresis loop, namely, combining other AFE
ceramics and BNT-based relaxor ferroelectric to prepare
composite materials.404 As an example, 0.96NN-0.04CaZrO3 was
selected as AFE ceramics to construct a 0–3 type composite
ceramic with 0.94(Na0.82K0.18)1/2Bi1/2TiO3-0.06FeNbO4 (NKBT-
FN) ceramics. As shown in Fig. 29g, pure NKBT-FN ceramic
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has a pinched P–E hysteresis loop due to the nonergodic relaxor
state,405 which is not ideal for energy storage. Aer incorpo-
rating 0.96NN-0.04CaZrO3, the P–E hysteresis loop gradually
becomes narrow and oblique, and a double P–E hysteresis loop
can be obtained with a concentration of 0.96NN-0.04CaZrO3
larger than 20 wt%. The observed linear P–E hysteresis loop in
0.96NN-0.04CaZrO3 can be ascribed to the inefficient electric
eld, which is lower than the driving eld for the AFE-FE phase
transition, as shown in Fig. 29i. This phenomenon also revealed
that the electric eld for the AFE-FE phase transition of 0.96NN-
0.04CaZrO3 ceramics can be minimized by embedding in
a relaxing matrix. Eventually, a high Wrec of 2.85 J cm3 and
a high h of 80% were obtained in the NKBT-FN/0.96NN-
0.04CaZrO3 ceramics with a mass ratios of 70/30 under 180
kV cm1.
4.4.5 Design strategies to enhance the dielectric break-
down strength. As mentioned above, high Eb is essential for
BNT-based ceramics to produce high Wrec. In order to improve
the Eb of BNT-based ceramics, the widely used approach is to
optimize the microstructure, such as increasing density,
decreasing grain size and reducing porosity, by doping sintering
aids such as ZnO, MgO, CuO, SiO2, SiO2–B2O3, BaCu(B2O5),
H3BO3, Dy2O3 and B2O3–Bi2O3–ZnO–SiO2 or using advanced
preparation methods such as microwave sintering and wet-
chemical method.346,348,364,388,401–403,409–411 The effect of the
dopants can be divided into two types. For example, the doping
of MgO usually increases the density and uniformity of the grain
distribution, as shown in Fig. 30a and b. As a result, the Eb of
0.475BNT-0.525Ba0.85Ca0.15Ti0.9Zr0.1O3 ceramics was enhanced
from 90 kV cm1 to 156.7 kV cm1 aer incorporating 0.5 wt%
MgO.409 Differently, the increased Eb in SiO2 modied
0.475BNT-0.525Ba0.85Ca0.15Ti0.9Zr0.1O3 ceramics usually comes
from the decreased grain size. As Fig. 30c–f shows, the grain size
Fig. 31 (a) h as a function of Wrec of different types of BNT-based ceramics. (b) A comparison of the Wrec and h among the widely studied (1  x)
BNT-xBT- and (1  x)BNT-xST-based ceramics. The data are from Tables 11, 12 and 13.
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of 0.95(0.76BNT-0.24ST)-0.05AN ceramics was decreased from
4.45 mm to 0.37 mm through introducing nano-SiO2, resulting an
enhanced Eb from 120 kV cm1 to 316 kV cm1. Correspond-
ingly, the Wrec was enhanced from 1.42 J cm3 to 3.22 J
cm3.378,402 A similar phenomenon is also observed in 0.9BNT-
0.1 KN ceramics. For pure 0.9BNT-0.1 KN ceramics, the Eb is
only 104 kV cm1, leading to a low Wrec of 1.17 J cm3.412 Aer
introducing SiO2 and optimizing the preparation process, the Eb
of 0.9BNT-0.1 KN ceramics was enhanced to
180 kV cm1 due
to the rened grains by Huang et al., resulting in a Wrec of 2.25 J
cm3.406 A macrostructure design was also used to increase the
Eb of BNT-based ceramics by embedding linear-like ceramics
with a high Eb.413 As Fig. 30g displays, the ferroelectric ceramics
and the linear-like ceramics were selected as the outer layer and
the middle layer, respectively. Fig. 30h shows photographs of
the prepared samples. The sandwich structure was conrmed
by cross-section SEM images (see Fig. 30i–k). By optimizing the
number of layers between ferroelectric ceramics and linear-like
ceramics, the composite ceramics simultaneously exhibit the
large Pmax of ferroelectric ceramics and the high Eb of the linear
ceramics, leading to a high Wrec of 6.78 J cm3 under 572
kV cm1.
In contrast to the traditional concepts of chemical compo-
sition or microstructure engineering, Li et al. proposed a grain
orientation engineering approach and implemented templated
grain growth to enhance the Eb.47 During the dielectric break-
down process, the strain induced by the electric eld also plays
an important role due to the fragile characteristics of dielectric
ceramics. In the case of perovskite crystals, the <111> direction
exhibits the minimum electrostriction compared to other
directions such as <100> and <110>, which can minimize the
strains and elastic energies caused by external electric elds.
Finite-element simulations have shown that the local
displacements, stresses and elastic energies of <111>-textured
samples are substantially lower than that of <100>-textured
ceramics. Benecial to low strain under external electric eld,
a decreased failure probability and an ultrahigh Eb were ach-
ieved in <111>-textured 0.65BNT-0.35Sr0.7Bi0.2TiO3 ceramics.
Based on the route of preparing bulk ceramics, non-textured
MLCC and textured MLCC, the Eb of (1  x)BNT-xSr0.7Bi0.2-
TiO3 dielectrics was improved from 200 kV cm1 of bulk
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Fig. 32 Schematic diagram of the tailoring strategy of AN-based ceramics.
ceramics to 640 kV cm1 of non-textured MLCC and nally to
1000 kV cm1 of textured MLCC, resulting in an ultrahigh Wrec
of 21.5 J cm3.
4.4.6 Summary of BNT-based ceramics. BNT is one of the
most thoroughly investigated energy-storage material systems
due to its large DP and wide range of adjustments of physical
properties. Currently, the research on BNT-based materials
focuses mainly on the construction of MPB followed by chem-
ical modication, or the development of relaxor-
antiferroelectric ceramics. Fig. 31 presents the h as a function
of Wrec of these three types of BNT-based ceramics. Both the
rst-type MPB and second-type MPB have a wide variation in
their energy storage characteristics depending on the other ions
or the third compound. Compared to the rst type, improved h
can be achieved in the second type MPB, i.e. rhombohedral and
pseudocubic phases, aer the introduction of suitable addi-
tional compounds. However, their energy storage performance
is still relatively poor (Wrec < 4 J cm3), and the recently devel-
oped relaxor antiferroelectric ceramics should be a promising
approach to further boost their energy storage performance. In
addition, a general criterion for developing BNT-based relaxor
antiferroelectric materials needs to be developed in future
research. Fig. 32b presents a comparison of the Wrec and h
among the widely studied (1  x)BNT-xBT- and (1  x)BNT-xST-
based ceramics. It can be found that although a high h can be
achieved in some compositions of (1  x)BNT-xBT-based
ceramics, the relatively low Eb (<200 kV cm1) leads to a low
Wrec (<2.5 J cm3) in spite of a large DP. In contrast, (1  x)BNT-
xST-based ceramics usually exhibit an ergodic relaxor state and
a moderate Eb (
250 kV cm1), demonstrating greater potential
for high energy storage.
5. Antiferroelectric ceramics
5.1 AgNbO3 (AN)-based ceramics
5.1.1 Physical properties and design strategy. AN, as a lead-
free antiferroelectric ceramic, shows great promise for electrical
energy storage due to its double P–E hysteresis loops with
a large polarization.414,415 With increasing temperature, AN
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undergoes a series of phase transitions: M1 / M2 / M3 / O1
/ O2 / T / C (see Fig. 33e), where M1, M2 and M3 represent
orthorhombic phases in rhombic orientation, O1 and O2 are
orthorhombic phases in parallel orientation, T is the tetragonal
phase and C is the cubic phase. Additionally, M1 is a ferrielectric
(FIE) phase, while M2 and M3 are AFE phases. Due to the diffi-
culty of manufacturing high-quality bulk ceramics, the energy
storage properties of AN-based ceramics were not reported until
2016 by Tian et al.415 A Wrec of 2.1 J cm3 was achieved in pure
AN ceramics under 175 kV cm1.415 However, the non-zero Pr,
resulting from the FIE phase at room temperature, coupled with
the apparent hysteresis antiferroelectricferroelectric transi-
tion leads to a relatively low h (<70%). Fig. 32 presents a sche-
matic diagram of the design strategy for AN-based ceramics. To
improve their energy storage performance, the chemical
modication of A-sites doping, B-sites doping or A and B-sites
co-doping was carried out to increase the stability of the AFE
phase by decreasing the tolerance factor or the polarity of B-site
ions, resulting in an increased antiferroelectric–ferroelectric
transition electric eld (EF), an enhanced ferroelectric-
antiferroelectric transition electric eld (EA), a decreased DE
(DE ¼ EF  EA) and a reduced Pr.60,416
5.1.2 Chemical modication to stabilize the anti-
ferroelectric phase. Table 14 summarizes the energy storage
properties of AN-based bulk ceramics. On the one hand, to
stabilize the AFE phase, Zhao et al. adopted Ta to decrease the
polarity of B-site ions (polarity Ta5+: 2.82 Å3, Nb5+: 3.10 Å3).45 As
shown in Fig. 33f, the M2 AFE phase was gradually tailored to
room temperature with increasing Ta concentration, indicating
an enhanced stability of the AFE phase at room temperature. As
a result, an increased EF and EA and a decreased DE with
a narrowed P–E hysteresis loops were achieved in AgNb0.85Ta0.15
ceramics (Fig. 33a and b), resulting in a high Wrec of 4.2 J cm3
and a h of 69% under 240 kV cm1. On the other hand, the
stability of the AFE phase can be achieved by decreasing the
tolerance factor (t), which is expressed by the following
equation:417
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Fig. 33 (a) P–E hysteresis loop and the associated I–E loop of pure AN ceramics. (b) P–E hysteresis loops of AN and Ag(Nb0.85Ta0.15)O3 ceramics.
(c) P–E hysteresis loops of Ag13xGdxNbO3 ceramics. (d) P–E hysteresis loops (SmxAg13x)(Nb0.9Ta0.1)O3 ceramics. (e) Temperature and
frequency dependence of 3r of AN ceramics. (f) Phase diagram of Ag(Nb1xTax)O3 determined from 3r. (g) The critical switching field EA and EF of
Ag13xLaxNbO3 ceramics. (h) Percentage variation of dielectric constant at low field in Ag13xBixNbO3 ceramics measured at 1 kHz. (i) Micro-
structure and (l) Eb and grain size of Ag13xLaxNbO3 ceramics. (a), (g), (i) and (l) Reproduced from ref. 418 with permission from The Royal Society
of Chemistry. (b), (e) and (f) Reprinted with permission from ref. 45. Copyright 2017 John Wiley and Sons. (c) Reproduced from ref. 421 with
permission from The Royal Society of Chemistry. (d) Reproduced from ref. 321 with permission from The Royal Society of Chemistry. (h)
Reproduced from ref. 419 with permission from The Royal Society of Chemistry.

Table 14 Summary of energy storage properties of AN-based bulk ceramics

Composition Wrec (J cm3) h (%) Pmax (mC cm2) Pr (mC cm2) EF (kV cm1) EA (kV cm1) Eb (kV cm1) Ref.

AN 2.1
42
6 125 50 175 415

Ag0.91Bi0.03NbO3 2.6 86
27
0
180
140 200 419
Ag(Nb0.85Ta0.15)O3 4.2 69 36.8 1.7 189 130 233 45
Ag0.97La0.01NbO3 + MnO2 3.0 51 44.5 3.5 142 86
180 422
Ag0.94La0.02NbO3 4.4 73
28
0.8 260 175 273 418
Ag0.96Ba0.02NbO3 2.3 36
36
2.5
143
68 180 423
Ag0.9Sr0.05NbO3 2.9 56
37.5
1.25
125
75 190 424
Ag0.88Gd0.04NbO3 4.5 64
37
5
255
170 290 421
Ag0.92Ca0.04NbO3 3.55 56.3 39.6
2 179 98 220 120
Ag0.91Sm0.03NbO3 5.2 68.5 38.4
2.1
220
145 290 420
Ag0.97Lu0.01NbO3 3.5 53.1 39.7
2.7
155
90 210 425
Ag0.97Nd0.01NbO3 3.2 52
42
3.5 149 74 210 426
0.45AN-0.55AgTaO3 6.3 90
29
1.5 330 270 470 322
Ag0.97Nd0.01Ta0.2Nb0.8O3 6.5 71
40
2
245
195 370 416
(Sm0.02Ag0.94)(Nb0.9Ta0.1)O3 4.87 63.5 38.5
2
220
140 280 321
0.994AN-0.006BiMnO3 2.4 54
37
3
126
70 175 427
0.99AN-0.01Bi(Zn2/3Nb1/3)O3 4.6 57.5 53.8 7.0 198 118 220 428
0.97AN-0.03BNT + MnO2 3.4 62
39
3.5
191
112 220 429
0.98AN-0.02CaTiO3 + MnO2 3.7 52.5
43
3
190
93 235 430
AN + MnO2 2.5 57 38.5 1 117 63 150 431
AN + WO3 3.3 50
43
1 165 75 200 432

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Fig. 34 (a) Temperature dependence of the 3r of AN with a series of phase transitions. Schematic diagram of P–E hysteresis loops for energy
storage of (b) a metastable AFEs with phase in M1 region, (b) fully stabilized AFEs with phase in M2 region, (d) fully stabilized AFEs with relaxor
characteristics around M2-M3 phase boundary. (e) Schematic phase diagram based on the temperature-dependent 3r. (f) 3r and dielectric loss of
ANT55 ceramic over the temperature range from 180 to 100  C. (g) P–E hysteresis loops and (h) composition-dependent energy storage
properties of ANTx ceramics. (a)–(h) Reprinted with permission from ref. 322. Copyright 2020 Springer Nature.

RA þ RO can lead to a low tolerance factor. To achieve this, various ions

t ¼ pffiffiffi
2ðRB þ RO Þ
where RA, RB and RO represent the radius of the A-site cations, B-
site cations and oxygen ions in the ABO3 perovskite structure,
respectively. Based on eqn (11), either decreasing the radius of
the A-site cations or increasing the radius of the B-site cations
(11)
were adopted to partly replace Ag+ (1.48 Å), including Gd3+
(1.053 Å), Sm3+ (1.24 Å), Bi3+ (1.17 Å) or La3+ (1.36 Å).418–421
Fig. 33c shows the P–E hysteresis loops of Ag13xGdxNbO3
ceramics. As shown, the phase transition eld of EA and EF
gradually increases with increasing the concentration of Gd
owing to the enhanced AFE stability. A large Wrec of 4.5 J cm3

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Fig. 35 (a) Wrec of AN-based ceramics as a function of the phase transition electric fields of EF and EA. (b) h as a function of Wrec of AN-based
ceramics.

and a h of 64% were achieved in Ag0.88Gd0.04NbO3 ceramics. In and Ta5+, respectively, both the tolerance factor and the polarity
addition, Han et al. used the strategy of A-/B-site co-doping to of B-site ions were decreased, leading to an enhanced stability
improve the energy storage performance AN-based ceramics, as of the AFE phase. Beneting from this, a high Wrec of 4.87 J
shown in Fig. 33d. Aer substitution of Ag+ and Nb5+ with Sm3+ cm3 and a h of 63.5% were achieved in

Fig. 36 Schematic diagram of four kinds of NN-based material types according to the characteristic of temperature dependence of 3r after
chemical modification.

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(Sm0.02Ag0.94)(Nb0.9Ta0.1)O3 under 246 kV cm1.321 Due to these
substitutions, beneting from the enhanced stability of the AFE
phase, an enhanced EF and EA, a reduced DE and Pr, a weak
dielectric nonlinearity, and a narrowed P–E hysteresis loop are
usually achieved in these solid solution (see Fig. 33b, g and
33h), which contribute to a high energy storage performance.
Also, the grain size of AN-based ceramics decreases with
increasing doping concentration (see Fig. 33i and l), leading to
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concentration of AgTaO3. Especially for ANT55 ceramic, the TM2-
M3 was tailored to room temperature, leading to a stabilized AFE
phase around room temperature. Also, a diffuse phase transi-
tion with frequency dispersion was observed in ANT55 ceramics
(see Fig. 34f), showing an obvious relaxor feature. Due to the
improved AFE phase stability and strong relaxation behavior,
the P–E hysteresis loops of ANTx ceramics gradually become
slim with the concentration of AgTaO3 increases, as shown in
Fig. 34g. Eventually, both a high Wrec of 6.3 J cm3 and a h of

a high Eb. The energy storage properties of some typical AN-

based ceramics are shown in Table 14. It can be found that
although the Wrec of AN-based ceramics has been improved
from 2.1 J cm3 of pure AN ceramics to 6.5 J cm3 of Ag0.97-
Nd0.01Ta0.2Nb0.8O3 ceramics, the h of these materials is still
relatively low (<70%), which needs to be further enhanced.
5.1.3 Designing AN-based antiferroelectrics with enhanced
relaxation behavior. Recently, Luo et al. proposed a strategy for
designing AN-based ceramics with stabilized antiferroelectricity
and enhanced relaxor behavior to achieve both a high Wrec and
a high h.322 The schematic diagrams are shown in Fig. 34a–d.
Pure AN ceramics exhibit a metastable AFE phase in the M1
region at room temperature. In this state, the large Pr and large
hysteresis result in a low Wrec and a low h (see Fig. 34b). Aer
introducing suitable ions to the A-site or B-site, the stable AFE
M2 and M3 phases can be shied to room temperature, leading
to a stabilized antiferroelectricity. In this state, AN-based
ceramics possess a low Pr and medium hysteresis, leading to
a medium Wrec and a medium h (see Fig. 34c). On this basis, if
the hysteresis can be further reduced through introducing
relaxor features, both a high Wrec and a high h can be expected
in AN-based ceramics (see Fig. 34d). Luo et al. selected (1  x)
AgNbO3-xAgTaO3 (ANTx) ceramics to validate the feasibility of
this strategy. As Fig. 34e shows, the M2-M3 phase transition
temperature (TM2-M3) gradually decreases with increasing
90% were obtained in ANT55 ceramics under 470 kV cm1,
which is superior to other AN-based ceramics.
5.1.4 Summary of AN-based ceramics. For AN-based
ceramics, the research mainly focuses on stabilizing the anti-
ferroelectric phase through chemical doping, and some great
achievements have been obtained. Beneting from the stable
anti-ferroelectric phase, AN-based ceramics usually exhibit
a high Pmax and a low Pr, together with enhanced phase tran-
sition electric elds of EF and EA, contributing to achieve a high
Wrec, as shown in Table 14. Fig. 35a presents the Wrec of AN-
based ceramics as a function of the phase transition electric
elds of EF and EA. As shown, a high Wrec is usually obtained in
AN-based ceramics with both a large EF and a large EA. Hence,
further increasing the EF and EA would be a good method to
achieve a higher Wrec. However, synthesizing high-quality AN-
based ceramics is still a challenging task due to the instability
of Ag2O, making most of the AN-based ceramics show a low Eb
(<250 kV cm1). In this case, breakdown occurs before reaching
the phase transition eld in spite that some samples exhibit
a high EF. So, in future research, the sintering process of AN-
based ceramics should be further optimized together with the
exploration of new fabrication methods. Despite of a high Wrec,
AN-based ceramics usually exhibit a low h (<75%) because of the
large hysteresis loss for the phase transition processes, as

Table 15 Summary of energy storage properties of NN-based bulk ceramics

Material
type Composition Wrec (J cm3) h (%) Pmax (mC cm2) Pr (mC cm2) Eb (kV cm1) 3r Ref.

AFE 0.96NN-0.04CaZrO3 0.55 63
9
1.2 130 270 320

NaNb0.4Ta0.6O3 0.9 87
13
1 160 700 463
0.9NN-0.06BaZrO3-0.04CaZrO3 1.59 30
32
5
225 464
RFE 0.77NN-0.23BT+Bi2O3 1.5 68.2 25 3.6 175 1900 449
Na0.7Bi0.1NbO3 4.03 85.4 37.5 1.1 250 1675 121
0.8NN-0.2ST 3.02 80.7 34.5 1.6 310 1450 465
0.85NN-0.15Bi(Zn2/3Nb1/3)O3 1.22 73.5
15
2 220 1050 457
0.91NN-0.09Bi(Zn0.5Ti0.5)O3 2.2 62.7 34.6 3.5 250 1070 466
0.93NN-0.07Bi(Mg0.5Zr0.5)O3 2.31 80.2
23
2.5 255 1125 460
0.9NN-0.1Bi(Mg2/3Nb1/3)O3 2.8 82
25
2 300 750 459
0.78NN-0.22Bi(Mg2/3Ta1/3)O3 5.01 86.1 18.5 1.42 627 350 455
0.92NN-0.08Bi(Mg0.5Ti0.5)O3 3.12 74
30
2.5 250 1300 462
0.88NN-0.12Bi(Zn0.5Zr0.5)O3 3.14 84.5 23.5 2 340 1000 454
0.91NN-0.09Bi(Zn0.5Ti0.5)O3 2.1 76 29.4 2.9 200 1800 453
0.68NN-0.32Ba0.6(Bi0.5K0.5)0.4TiO3 2.75 78.3
32
4 290 1850 451
0.86NN-0.14(Bi0.5Na0.5)HfO3 3.51 80.1 24.49 1.97 350 800 126
(Na0.84Bi0.08)(Nb0.92Zr0.08)O3 2.5 92
23
0 260 970 467
(Na0.84Bi0.08)(Nb0.92Zr0.08)O3+CuO 4.9 88
32
0.5 430 467
RAFE 0.92NN-0.08Bi(Mg0.5Ti0.5)O3+MnO2 5.57 71
40
0 480 1000 462
(Na0.91La0.09)(Nb0.82Ti0.18)O3 6.5 66
43
7 550 880 461
0.76NN-0.24BNT 12.2 69
62
7 680 1350 46

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shown in Fig. 35b. Although both a high Wrec and a high h can
be expected in some compositions through introducing relax-
ation characteristic to reduce the hysteresis effect, the strong
relaxation behavior will result in a large driving eld of EF,
which is challenging for most AN-based ceramics. If the sample
can achieve the phase transition, appropriately increasing the
relaxation characteristics should be a good strategy to design
high-performance AN-based ceramics. The systematic chemical
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electrical energy storage in recent years. With decreasing
temperature, NN undergoes several phases transition due to the
tilted oxygen octahedral and off-centered Nb5+ ions:433,434 U
(cubic, Pm3m-) / T2 (tetragonal, P4mbm-) / T1 (orthorhombic,
Ccmm-) / S (orthorhombic, Pnmm-) / R (orthorhombic,
Pmnm-) / P (orthorhombic, Pbma-) / N (rhombohedral, R3c-),
where N is ferroelectric, P and R phases are AFE phase, S, T1, T2,
and C phases are paraelectrics. Although NN ceramic exhibit

modication method for designing AN-based antiferroelectric
ceramics with enhanced relaxation behavior requires further
investigation. Furthermore, most of the studies are related to
AN-based bulk ceramics and there is no report about AN-based
MLCC, which should receive more attention in subsequent
research.
5.2 NaNbO3(NN)-based ceramics
5.2.1 Physical properties. NN ceramic, as a promising lead-
free AFE material, has received considerable attention for
several phase transition, the usually observed dielectric
anomaly from the dielectric temperature spectrum is the AFE
phase transition from P to R at around 370  C. In addition, the
AFE P phase in NN ceramics is not very stable, which irreversibly
changes to a ferroelectric phase Q (P21ma) at room temperature
under external electric elds due to their similar free ener-
gies.435–437 As a result, the usually observed P–E hysteresis loops
for pure NN ceramic is a square P–E hysteresis loop instead of
a double P–E hysteresis loop, leading to a low Wrec and a low h.

Fig. 37 (a) Tolerance factor versus averaged electronegativity difference for (Na1xAx2+)(Nb1xBx4+)O3 composition, where (A,B) ¼ (Ca,Zr),
(Ca,Hf), (Sr,Zr) and (Sr,Hf). (b) P–E hysteresis loops of the (Na1xCax)(Nb1xZrx)O3 (CZNN) ceramics at 120  C. (c) P–E hysteresis loops of the
0.96NN-0.04CaZrO3 (NN-4) ceramics at room temperature. (d) Temperature dependence of P–E hysteresis loops with the corresponding J–E
curves for a few (0.94  x)NN-0.06BaZrO3-xCaZrO3 ceramics. (a) and (b) Reproduced from ref. 438 with permission from The Royal Society of
Chemistry. (c) Reprinted with permission from ref. 320. Copyright 2018 Elsevier. (d) Reprinted with permission from ref. 464. Copyright 2019
Elsevier.

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5.2.2 Classication of NN-based materials. According to
the characteristic temperature dependence of 3r aer chemical
modication, NN-based ceramics can be divided into four
kinds, as shown in Fig. 36. For the rst kind of material, the
phase transition temperature gradually decreases with
increasing the secondary compound, accompanied with the
decrease of 3r. The commonly used doping compounds include
CaZrO3, CaTiO3, BaZrO3, CaHfO3 and SrZrO3.320,438–443 For these
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materials, the solubility is usually less than 10 mol%. Aer
chemical modication, the AFE phase of NN ceramics can be
stabilized, showing a double P–E hysteresis loop under certain
conditions (see Fig. 36). Due to the large hysteresis and the low
Eb, this kind of material usually exhibits a low Wrec and a low h.
The second kind of material is obtained through incorporating
BT.444–449 The dielectric peak becomes gradually diffuse and
more dependent on the testing frequency with increasing BT
concentration, showing a typical relaxor characteristic. Mean-
while, the maximum 3r is signicantly enhanced aer intro-
ducing BT. (1  x)NN-xBT ceramics enter into an ergodic relaxor
state when x $ 0.23. However, the strong dielectric nonlinearity
makes that the polarization of this kind of material tends to
saturate at a low electric eld, leading to a moderate Wrec. For
the third kind of material, Tm decreases smoothly with
increasing amount of secondary ions or compounds before the
concentration reaches a threshold. Above the threshold, the
ferroelectric phase becomes stable accompanied by an abrupt
drop of the Tm value.450 The threshold is usually around 5 mol%,
depending on the type of the secondary compound. Also,
a diffuse phase transition together with frequency dispersion of
Fig. 38 Schematic diagram of NN-based relaxor ferroelectrics. (a) Four different temperature regions of typical relaxor ferroelectrics. (b) Domain
structure and P–E hysteresis loops of typical relaxor ferroelectrics in different temperature regions.
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3r can be observed in these materials, featuring a strong relax-
ation behavior. This kind of material can be obtained through
incorporating ST, (Bi0.5Na0.5)HfO3, Bi(Mg0.5Ta0.5)O3, Bi(Ni0.67-
Ta0.33)O3, and Ba(Mg0.5Nb0.5)O3, etc.126,451–460 Compared with the
second kind of material, weak dielectric nonlinearity can be
expected in the third kind material, resulting in nearly linear
polarization behavior under a low electric eld. However, the
addition of a secondary compound will deteriorate the 3r
(<1000), hence a large Eb is usually required to obtain a high
Wrec for this kind of material. The fourth kind of material is
relaxor antiferroelectric ceramics. Up to now, (Bi0.5Na0.5)TiO3,
(La0.5Na0.5)TiO3 and Bi(Mg0.5Ti0.5)O3 have been conrmed to be
effective dopants to induce the relaxor antiferroelectric char-
acteristic in NN ceramics.46,461,462 Aer doping, the Tm gradually
decreases, and the dielectric spectrum exhibits an obvious
diffuse phase transition and frequency dispersion under high
doping concentration. It should be noticed that the AFE phase
can be maintained under a high doping concentration for this
kind of material. Since these materials can couple the respective
advantages of relaxor ferroelectric materials (low hysteresis
loss) and anti-ferroelectric materials (high Pmax and low Pr), an
ultrahigh Wrec can be obtained in these ceramics under a high
electric eld. Table 15 summarizes the energy storage perfor-
mance of different types of NN-based ceramics. The detailed
design strategies for each type of material are discussed below.
5.2.3 NN-based antiferroelectric ceramics. For the rst type
of NN-based materials, the research concentrates on stabilizing
the AFE phase through chemical modication. For instance,
Shimizu et al. proposed a strategy of decreasing the tolerance
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factor while keeping the electronegativity difference (X) to
stabilize the AFE phase in NN-based ceramics.438 Based on this
principle, they predicted several compositions that might
stabilize the AFE phase in NN ceramics (see Fig. 37a), and then
selected (Na1xCax)(Nb1xZrx)O3 as an example to investigate. It
was found that the stability of the AFE phase can be enhanced
by increasing the substitution of Zr4+ and Ca2+ ions in the Nb
and Na sites, respectively, owing to the decreased tolerance
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stabilize the AFE phase in NN ceramics.464 With increasing
concentration of CaZrO3, the phase evolved from an instable
AFE phase to an orthorhombic AFE P phase (Pbma), and double
P–E hysteresis loops were observed in (0.94  x)NN-0.06BaZrO3-
xCaZrO3 ceramics at room temperature together with the
emergence of four current peaks when x $ 0.02. Meanwhile, the
phase transition eld of EF gradually increased accompanied by
an decreased Pr value due to the increased stability of AFE

factor, but the double P–E hysteresis loop can only be induced at
a high temperature of 120  C (see Fig. 37b). Later, a double P–E
hysteresis loop of 0.96NN-0.04CaZrO3 ceramics at room
temperature was obtained by Liu et al. via optimizing the
preparation process, as shown in Fig. 37c.320 Apart from the
enhanced stability of the AFE phase, the incorporation of
CaZrO3 can decrease the number of defects in NN ceramics,
resulting in an improved Eb. A Wrec of 0.55 J cm3 and a h of 63%
was achieved in 0.96NN-0.04CaZrO3 under 130 kV cm1. In
addition, Qi et al. employed BaZrO3 together with CaZrO3 to
phase, as shown in Fig. 37d. Beneting from the stable AFE
phase, a Wrec of 1.59 J cm3 was achieved in 0.90NN-0.06BaZrO3-
0.04CaZrO3 ceramics, but the large hysteresis between the
phase transition processes results in a low h of 30%.
5.2.4 NN-based relaxor ferroelectric ceramics. Although
double P–E hysteresis loops can be achieved in NN-based
ceramics, the large hysteresis leads to a low Wrec and a low h.
To further improve the energy storage performance, a series of
NN-based relaxor ferroelectrics were developed. For (1  x)NN-
xBT ceramics, the low Eb and strong dielectric nonlinearity lead

Fig. 39 (a) Temperature dependence of the 3r and dielectric loss, (b) P–E hysteresis loops at different electric fields and (c) Wst, Wrec and h at
different electric fields for the Na0.7Bi0.1NbO3 ceramics. (d) Temperature dependence of the 3r and dielectric loss, (e) P–E hysteresis loops at
different electric fields and (f) Wrec and h at different electric fields for 0.86NN-0.14(Bi0.5Na0.5)HfO3 ceramics. (g) Temperature dependence of the 3r and
dielectric loss, (h) P–E hysteresis loops at different electric fields and (i) Wch, Wrec and h at different electric fields for 0.9NN-0.1Bi(Mg2/3Nb1/3)NbO3
ceramics. (a)–(c) Reproduced from ref. 121 with permission from The Royal Society of Chemistry. (d)–(f) Reproduced from ref. 126 with permission from
The Royal Society of Chemistry. (g)–(i) Reproduced from ref. 459 with permission from The Royal Society of Chemistry.

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to a low Wrec. Although the Eb was signicantly enhanced aer
doping 1.5 mol% Bi2O3, the obtained Wrec was still less than 2 J
cm3.449 Later, researchers designed various relaxor ferroelec-
trics with weak dielectric tunability through incorporating
suitable other ions or a secondary compound such as Bi3+, ST,
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Bi(Zn0.5Ti0.5)O3, Bi(Mg0.5Zr0.5)O3, (Bi0.5Na0.5)HfO3, Bi(Mg2/3Nb1/3)
O3 and Bi(Ni0.67Ta0.33)O3 etc.121,126,449,451,453,458–460,465–468 The design
strategy of these solid solutions is shown in Fig. 38. For typical
relaxor ferroelectrics, there exist three characteristic temperatures,
e.g., TB, Tm and Tf, where TB is the Burns temperature, Tm is the

Fig. 40 (a) Sketch of the evolution of P–E hysteresis loops and energy storage properties with enhancing the AFE phase stability and introducing
relaxor features in NN-based ceramics. (b) P–E hysteresis loops and the corresponding J–E curves and (c) Wrec and h values for the (Na0.91-
La0.09)(Nb0.82Ti0.18)O3-0.01BaCu(B2O5) ceramic under different electric fields and at room temperature. (d) P–E hysteresis loops and the cor-
responding J–E curves and (e) Wrec and h values for the 0.76NN-0.24BNT ceramic under different electric fields and at room temperature. (a)–(c)
Reprinted with permission from ref. 461. Copyright 2020 American Chemical Society. (d) and (e) Reprinted with permission from ref. 46.
Copyright 2019 John Wiley and Sons.

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temperature corresponding to the maximum 3r and Tf is the
freezing temperature.79,469–471 Based on these three characteristic
temperatures, the curve of temperature dependence of the 3r of
relaxor ferroelectric can be divided into four distinct regions, as
shown in Fig. 38a. Each region exhibits its unique domain
structures, dielectric and ferroelectric properties, resulting in
different energy storage performance, as shown in Fig. 38b.
Nanodomains and PNRs are usually formed in relaxor ferro-
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electrics in region 2. Due to the low energy barriers and high
dynamics of nanodomains and PNRs, slim P–E hysteresis loops
with near-linear polarization response are usually observed in
this region. Also, relaxor ferroelectrics in this region exhibit
a moderate 3r with low dielectric nonlinearity and weak
temperature sensitivity, which is conducive to a large DP. Based
on the above discussion, slim P–E hysteresis loops, large DP and
high Eb could be expected in relaxor ferroelectrics in region 2,
contributing to both a high Wrec and a high h. In some litera-
ture, relaxor ferroelectrics in region 2 are also called crossover
relaxor ferroelectrics.131,234 Therefore, tailoring the temperature
region between Tm and TB to room temperature should be
a good strategy for relaxor ferroelectrics to concurrently achieve
a large Wrec and a high h.472,473
The energy storage performance of NN-based relaxor ferro-
electrics was rst reported by Zhou et al. in 2018. As shown in
Fig. 39a, the temperature range from Tm to TB of NN ceramics
was tailored to room temperature through incorporating Bi2O3,
leading to a slim P–E hysteresis loops with a low Pr (see Fig. 39b).
Meanwhile, the incorporation of Bi2O3 promotes the sintering
process and then leads to a dense microstructure, which is in
favor of a high Eb. As a result, a high Wrec of 4.03 J cm3 and a h
of 85.4% were achieved in Na0.7Bi0.1NbO3 under 250 kV cm1
(see Fig. 39c). Yang et al. employed (Bi0.5Na0.5)HfO3 to tailor the
energy storage performance of NN ceramics.126 A wide temper-
ature range between Tm and TB was tailored to room tempera-
ture in 0.86NN-0.14(Bi0.5Na0.5)HfO3 ceramics, as shown in
Fig. 39d. As a result, a high Wrec of 3.51 J cm3 together with
a high h of 80.1% was achieved in 0.86NN-0.14(Bi0.5Na0.5)HfO3
ceramics under 350 kV cm1 (see Fig. 39e and f). The energy
storage performance of 0.86NN-0.14(Bi0.5Na0.5)HfO3 ceramic
also exhibits excellent thermal stability over 20  C to 200  C. A
similar phenomenon is also observed in Bi(Mg2/3Nb1/3)NbO3
modied NN ceramics (see Fig. 39g).459 Apart from the induced
Fig. 41 (a) Wrec versus Eb of different types of NN-based ceramics. (b) h versus Wrec of different types of NN-based ceramics.
This journal is © The Royal Society of Chemistry 2021
View Article Online
Journal of Materials Chemistry A
slim P–E hysteresis loops (see Fig. 39h), the incorporation of
Bi(Mg2/3Nb1/3)NbO3 apparently decreases the dielectric loss and
suppresses the grain growth, resulting in a high Eb of 300
kV cm1. Finally, a large Wrec of 2.8 J cm3 with a high h of 82%
was obtained in 0.9NN-0.1Bi(Mg2/3Nb1/3)NbO3 ceramics.
5.2.5 NN-based relaxor-antiferroelectric ceramics. Even
though the h of NN-based relaxor ferroelectrics has been obvi-
ously improved, the Wrec of these materials remains relatively
low. Qi et al. developed a number of relaxor antiferroelectric
ceramics to further improve the Wrec. Fig. 40a illustrates the
design strategy of these materials. First of all, the h of NN-based
ceramics was enhanced by stabilizing AFE P phase. The large
hysteresis of the dual P–E hysteresis circuit however results in
a medium Wrec and a medium h. On this basis, the relaxor
feature was introduced in NN-based ceramics to narrow the P–E
hysteresis loops and enhance the driving eld of EF, leading to
both a large Wrec and a high h. According to this design strategy,
Chen et al. adopted La3+ to stabilize the AFE phase of NN
ceramics due to its smaller radius and larger electronegativity
compared with Na+ (La3+: 1.36 Å and 1.1 Å3, Na+: 1.39 Å and 0.93
Å3). In addition, Ti4+ ions were employed to substitute Nb5+ ions
to enhance the relaxation behavior. As a result, a slim double-
like P–E hysteresis loop with a high EF was obtained in
(Na0.91La0.09)(Nb0.82Ti0.18)O3 ceramics, showing a high Wrec of
6.5 J cm3 and a moderate h of 66% (see Fig. 40b and c).461
Another NN-based relaxor antiferroelectric ceramic was devel-
oped by Qi et al. via introducing BNT, as shown in Fig. 40d and
e.46 A record Wrec of 12.2 J cm3 and an medium h of 69% were
achieved in 0.76NN-0.24BNT ceramics under 680 kV cm1. For
these solid solutions, it should also be noticed that the incor-
poration of secondary compound and sintering aids can
signicantly reduce the dielectric loss and decrease the grain
size of NN ceramics, leading to an ultrahigh Eb (>500 kV cm1).
This should be an important reason for the obviously improved
energy storage performance, which guarantees the ferroelectric
phase of these relaxor antiferroelectric materials can be induced
before breakdown.
5.2.6 Summary of NN-based ceramics. Research on NN-
based ceramics has proceeded from typical antiferroelectric
materials to relaxor ferroelectric materials and then to relaxor
antiferroelectric materials. As the material type evolved, the Wrec
of NN-based ceramics has been greatly enhanced, in particular
J. Mater. Chem. A

Journal of Materials Chemistry A
for the recently developed relaxor antiferroelectric ceramics, as
shown in Fig. 41a. The enhancement of Eb plays an important
factor for the high Wrec. For example, the Eb of NN-based anti-
ferroelectric ceramics is usually below 150 kV cm1. Aer
developing relaxor ferroelectrics, a higher Eb of
300 kV cm1
can be achieved, while the Eb of relaxor antiferroelectric
ceramics can be increased to more than 500 kV cm1. Apart
from the difference in the inherent physical properties (band
Published on 23 July 2021. Downloaded by UNIVERSIDAD SAO PAULO on 8/13/2021 3:36:04 PM.
gap, electrostriction coefficient) of different materials, the
optimization of the preparation processes should be respon-
sible for the enhanced Eb, which leads to a dense microstructure
with a small grain size, a low dielectric loss and a high grain
boundary resistivity. In addition, although a high Wrec can be
obtained in some NN-based ceramics, the design and synthesis
of these materials are still at a primary stage and there are still
some issues to be solved. On the one hand, the h of most NN-
based ceramics is below 90% especially for relaxor antiferro-
electric ceramics in spite of a high Wrec, as shown in Fig. 41b.
Developing new NN-based ceramics with both a high Wrec and
a high h is still highly required. For the complex phase transi-
tion processes, the detailed crystal structure and phase transi-
tion temperature have not been fully understood. On the other
hand, the underlying principle of chemical modication to
develop different types of NN-based materials needs to be
further studied.
6. Summary and perspectives
The research on lead-free bulk ceramics for dielectric capacitors
is becoming more and more attractive because of their prom-
ising applications ranging from electronic circuits, hybrid cars
to integrated circuit, and great progress has been achieved in
the last ten years. In terms of material types, linear materials
have developed from the initial low 3r and high Eb to the current
high 3r and high Eb through incorporation of other ions or
developing linear/nonlinear composite materials. The research
on relaxor ferroelectrics has evolved from the original
enhancement of relaxation characteristics to the present
develop crossover relaxor ferroelectrics via carefully tailoring
the temperature range between Tm and TB to room temperature.
Both a high DP and a high Eb can be expected in this region,
leading to an optimal energy storage performance. In the case of
antiferroelectric ceramics, relaxor characteristics have been
introduced to design relaxor antiferroelectric ceramics in
addition to simply stabling the anti-ferroelectric phase.
Through this strategy, many antiferroelectric ceramics exhibit-
ing both a high Wrec and a high h have been obtained. The
tailoring strategy has evolved from singly developing new
materials or optimizing preparation processes to the latest
multi-scale optimization strategy from microstructure, material
composition to device design. Correspondingly, the design
scale changes from the centimeter level of device congurations
to the angstrom level of atomic structures. For specic mate-
rials, the research on BNT and BF-based ceramics mainly
concentrates on improving the Eb and depressing the Pr, while
stabilizing the antiferroelectric phase becomes extremely
important for AN and NN-based antiferroelectric ceramics. Also,
J. Mater. Chem. A
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Review
tailoring the grain size to submicron size has been carried out in
KNN-based ceramics to develop dielectric ceramics with a high
Eb and a series of BT-based relaxor ferroelectrics with
a moderate Wrec and a high h have been obtained via incorpo-
rating another perovskite compound. With the discovery of new
materials, the optimization of preparation processes and the
advancement of design strategies, the Wrec of bulk ceramics has
been enhanced from the original 1 J cm3 to present more than
10 J cm3, and the overall Wrec of MLCC has reached more than
20 J cm3.
Despite the enormous progress, there are still some prob-
lems for practical applications. Dielectric ceramics exhibiting
both a high Wrec (>4 J cm3) and a high h (>90%) are still rela-
tively few, which cannot meet the requirements of lightweight
and miniature advanced electronic and electric power systems.
In order to improve the energy storage performance, current
research mainly focuses on improve the DP and Eb. Specically,
the widely used strategies to improve the Eb include decreasing
the grain size, enhancing the uniformity of the grains,
promoting electrical homogeneity, increasing the resistance,
improving the thermal conductivity and reducing the dielectric
loss. These strategies can be achieved through adopting
advanced sintering methods, adding sintering aids, using two-
step sintering, optimizing the heating rate and holding time
or fabricating composite materials, while effective methods to
further improve the Eb are restricted. To break this bottleneck,
apart from optimizing these macro-physical properties, much
attention should be paid to control the micro characteristics
such as vacancy-related defects and micro stress. The vacancy-
related defects are usually generated during high-temperature
sintering or other ions doping. These defects will not only
increase the dielectric loss, but also can trap electrons upon
visible light illumination, decreasing the resistance. In addi-
tion, the micro stress can be formed in samples during rapid
cooling and thickness cutting processes, which promotes the
occurrence of electrical and mechanical failures. Although
these defects and micro stress can be reduced by adjusting the
composition, controlling the cooling rate or using later heat
treatment, advanced characterization methods are required to
qualitatively illustrate their impact on breakdown strength. It is
also necessary to study the breakdown process to demonstrate
which type of breakdown is dominant and where the break-
down usually occurs, which can give a guideline to further
enhance the Eb. To achieve a high DP, the commonly used
method is to select a host material with strong ferroelectricity,
and then reduce its Pr via composition doping, or choose a host
materials with a small Pr and then incorporate a secondary
compound such as Bi-based compounds to increase its Pmax.
However, it is still difficult to simultaneously achieve both
a high Pmax and a low Pr in these solid solutions. Although the
domain engineering makes it possible to develop dielectric
ceramics with both a low Pr and a moderate DP by inducing
nanodomains or PNRs, the Pmax value achieved in these mate-
rials is still relatively low, limiting the further enhancement of
Wrec. Recently proposed local region design strategy, namely,
designing local regions with different polarization-eld
response behavior or constructing local regions with
This journal is © The Royal Society of Chemistry 2021

Review
polymorphic PNRs through phase structure regulation would be
a good choice to develop dielectrics with both a high Pmax and
a low Pr. Also, some advanced characterization methods are
required to give an insight into the evolution process of the local
region under different temperatures or electric elds.
The problems of expensive raw materials, complex compo-
sition, harsh preparation conditions and poor repeatability of
dielectric ceramics make them difficult for quantity production.
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In practical terms, multilayer structures are employed, while the
high sintering temperature (>1100  C) of most dielectric
ceramics is not compatible with cheap base-metal electrodes
such as copper and nickel when fabricating MLCC, thus greatly
increasing the cost. Also, for some advanced applications,
dielectric capacitors are usually operated in the environment of
high temperature, high humidity and high applied electric eld.
Consequently, apart from improving the Wrec and h, the energy
storage performance of thermal stability, fatigue properties,
mechanical properties and reliability of dielectric ceramics also
need to be improved. Furthermore, standard test conditions for
the measurement of P–E hysteresis loops must be dened by
setting the sample thickness, electrode form, electrode eld,
test frequency, and medium type of insulating.
Developing dielectric ceramics with both a high Wrec and
a high h is still the future research direction. Furthermore, the
contradiction between the 3r and the Eb and the trade-off
between the Wrec and h also need to be reconciled. To achieve
these goals, in addition to continually explore new materials,
new manufacturing methods and new design strategies, more
studies are required to reveal the underlying mechanisms such
as sample sintering processes, dielectric breakdown processes
and dielectric polarization properties in local regions, and
eventually build a deeper understanding of the composition-
structure–property of dielectric ceramics for energy storage.
New tailoring strategies for each type of materials need to be
developed based on their unique physical properties and multi-
scale comprehensive design strategies are needed when
designing new materials in the future. In addition to optimizing
a single material, more attention should be paid to composite
materials including ceramic/ceramic composites, ceramic/glass
composites, ceramic/polymer composites and ceramic/glass/
polymer composites since it is challenging to design a single
material to meet all the requirements such as high Pmax, low Pr,
high Eb, low dielectric loss, good thermal stability and excellent
fatigue. For practical applications, dielectric ceramics featuring
a facile preparation process, a simple chemical composition
and a low sintering temperature are still highly desired. In
terms of the research method, a combination of advanced
synthesis (two-step sintering and pressure assisted sintering),
comprehensive characterizations (aberration-corrected scan-
ning transmission electron microscope and piezoelectric force
microscopy), multiple control strategies (nanodomain engi-
neering and grain size engineering) and theoretical calculations
(machine learning and phase-eld simulations) can be adopted
to design new materials.
This journal is © The Royal Society of Chemistry 2021
View Article Online
Journal of Materials Chemistry A
Conflicts of interest
There are no conicts to declare.
Acknowledgements
This work was supported by the Natural Science Basis Research
Plan in Shaanxi Province of China (Grant No. 2020JM-635), the
Youth Innovation Team of Shaanxi Universities and the Scien-
tic Research Initiation Funds for the Doctoral Program of Xi'an
International University (Grant No. XAIU2019001), Scientic
Research Program Funded by Shaanxi Provincial Education
Department (Program No.21JP104), and the National Nature
Science Foundation of China (Grant Nos. 51772239 and
51761145024). Zetian Yang thanks the invaluable support and
care of Yuehui Zhang over the years.
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