Novel Strontium Titanate-Based Lead-Free Ceramics for High-Energy

Sep 27, 2017 - Novel Strontium Titanate-Based Lead-Free Ceramics for High-Energy Storage Applications ... To achieve the miniaturization and integrati...
1 downloads 21 Views 2MB Size
Subscriber access provided by UNIV OF ESSEX

Article

Novel Strontium Titanate-based Lead-free Ceramics for High Energy Storage Applications Haibo Yang, Fei Yan, Ying Lin, and Tong Wang ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/ acssuschemeng.7b02203 • Publication Date (Web): 27 Sep 2017 Downloaded from http://pubs.acs.org on October 2, 2017

Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

ACS Sustainable Chemistry & Engineering is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

Page 1 of 31

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Sustainable Chemistry & Engineering

Novel Strontium Titanate-based Lead-free Ceramics for High Energy Storage Applications Haibo Yang*, Fei Yan, Ying Lin, Tong Wang

School of Materials Science and Engineering, Shaanxi University of Science and Technology, 710021, Weiyang District, Xi’an, China *Corresponding author. Email: [email protected]

ACS Paragon Plus Environment

ACS Sustainable Chemistry & Engineering

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 2 of 31

ABSTRACT: In order to achieve the miniaturization and integration of advanced pulsed power capacitors, it is highly desirable to develop lead-free ceramic materials with high recoverable energy density (Wrec) and high energy storage efficiency (η). Whereas, Wrec (< 2 J/cm3) and η (< 80%) have be seriously restricted because of low electric breakdown strength (BDS < 200 kV/cm) or small maximum polarization (Pmax). Composition control was used to enhance the Pmax and further obtain excellent energy

storage

properties

0.07Ba0.94La0.04Zr0.02Ti0.98O3)

in

our

study.

(1-x)SrTiO3-x(0.93Bi0.5Na0.5TiO3-

((1-x)ST-x(BNT-BLZT))

ternary

solid

solution

ceramics with x = 0.0-0.5 were fabricated using the tape-casting process and sintered by solid-state sintering method. All samples show slim polarization-electric field (P-E) loops. The composition of 0.8ST-0.2(BNT-BLZT) ceramic possesses excellent energy storage properties with a Wrec of 2.83 J/cm3 and a η of 85% simultaneously. The significantly enhanced Wrec (2.83 J/cm3) is almost 2 times higher than previous reported results of lead-free ceramics with η > 80%. The results indicate that (1-x)ST-x(BNT-BLZT) lead-free ceramics can be used for pulsed power capacitors and open up a new research of ST-based ceramics. KEYWORDS: Energy storage; Dielectric properties; Lead-free ceramics; SrTiO3 INTRODUCTION Dielectric capacitors have higher power density and charge-discharge rate compared with batteries and super-capacitors, and been widely used in pulsed power systems such as high power microwaves, electromagnetic armor and so on.1-7 In

ACS Paragon Plus Environment

Page 3 of 31

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Sustainable Chemistry & Engineering

contrast, ceramic dielectric materials possess excellent mechanical and thermal properties compared with polymer dielectric materials.8 Thus ceramic dielectric materials are considered to be the best potential candidate for pulsed capacitor applications. The electric energy storage density (W) for ceramic dielectric materials can be evaluated by Equation (1).6 

    

(1)

Where E is the applied electric field (kV/cm), P is the polarization (µC/cm2), and Pmax is the maximum polarization (µC/cm2). The value of W can be illustrated by green and blue area in Figure 1. As shown in Figure 1, the paths of charge and discharge are not coincident. Thus, energy delivered to the capacitor cannot be released completely. Take this into account, Wrec and η are important indicators of energy storage systems. The Wrec and η can be calculated according to Equation (2) and (3), respectively.6, 9 

      



 

 100%

Figure 1 Schematic for the calculation of energy storage properties.

ACS Paragon Plus Environment

(2) (3)

ACS Sustainable Chemistry & Engineering

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 4 of 31

Where Pr is the remnant polarization (µC/cm2). In order to achieve high Wrec and η, high BDS, large Pmax, small Pr and low Wloss are required. According to the previous work on energy storage ceramics, anti-ferroelectric ceramics have higher Wrec compared with ferroelectric ceramics and linear dielectric ceramics due to large Pmax, small Pr and moderate BDS.10-12 For example, Zhang et al. studied Y doping (Pb0.87Ba0.1La0.02)(Zr0.65Sn0.3Ti0.05)O3 ceramics and achieved a Wrec of 2.75 J/cm3 and a η of 71.5%.13 Xu et al. reported that a Wrec of 3.12 J/cm3 was obtained for ceramic.14

0.92Pb(Tm1/2Nb1/2)O3-0.08Pb(Mg1/3Nb2/3)O3

However,

most

of

anti-ferroelectrics are lead-based materials, which are not environmentally friendly. With the improvement of environmental quality and the requirements of human health, those environmentally hazardous materials need to be replaced by lead-free materials.15 Thus, the development of outstanding Wrec and η of lead-free ceramics is urgent in the field of pulsed power capacitors. Currently, BaTiO3 (BT)-based, (Bi0.5Na0.5)TiO3 (BNT)-based, (K0.5Na0.5)NbO3 (KNN)-based and SrTiO3 (ST)-based lead-free ceramics have attracted much attention for high energy storage applications.8,

16-18

BT-based and BNT-based lead-free

ceramics have been widely studied on energy storage due to large Pmax, but most of these lead-free ceramics do not possess high Wrec (> 2 J/cm3) and high η (> 80%), simultaneously, because of large Pr and low BDS.19,

20

For instance, Shen et al.

reported that a Wrec of 0.71 J/cm3 and a η of 71.5% could be obtained at 93 kV/cm in 0.91BaTiO3-0.09BiYbO3

ceramic.21

Xu

et

ACS Paragon Plus Environment

al.

obtained

the

Page 5 of 31

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Sustainable Chemistry & Engineering

0.90(0.92Bi0.5Na0.5TiO3-0.08BaTiO3)-0.10NaTaO3 ceramic with a Wrec of 1.2 J/cm3 and a η of 74.8% at 100 kV/cm.22 Recently, Wang et al. reported that the [(Bi0.5Na0.5)0.94Ba0.06]La(1-x)ZrxTiO3 ceramics have double P-E hysteresis loops, small Pr and large Pmax (37.5 µC/cm2), but the BDS is too low to obtain high energy storage properties (the maximum value of Wrec is only 1.58 J/cm3).23 KNN-based ceramics are more beneficial to be used for advanced pulsed power capacitors due to high Wrec (~ 4 J/cm3), but their value of η are lower than 65% because of larger Pr. A Wrec of 4.03 J/cm3 and a η of 52% were achieved for 0.85(K0.5Na0.5)NbO3-0.15SrTiO3 ceramic.24 Dielectric materials with lower η lose a higher amount of their stored energy to heat, and the generated heat would degrades the properties of dielectric materials.25 Meanwhile, the cost of raw materials for KNN-based ceramics is too expensive to be commercialized, and it is difficult to obtain KNN-based ceramics due to the fact that the sintering temperature range of KNN ceramics is extremely narrow.26-28 Therefore, for lead-free energy storage ceramic materials not only the excellent properties but also the cost and feasible mass-production fabrication process should also been considered. SrTiO3 (ST) needs relatively inexpensive raw materials, has broad sintering temperature range and can be used for mass-production for high-voltage capacitors.29 In addition, ST-based ceramics are also expected to be used for high energy storage capacitors. Because ST possesses unique physical properties, for instance, low dielectric loss (< 0.01) and favorable electric filed stability.30,

31

Meanwhile, ST belongs to linear dielectrics and has high value of η. Based on the

ACS Paragon Plus Environment

ACS Sustainable Chemistry & Engineering

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

above features, the Wrec and η of ST-based ceramics can be modified by the introduction of other components.32-34 For example, Xie et al. obtained a Wrec of 1.1 J/cm3 and a η of 87% in SrSn0.05Ti0.95O3 ceramic.11 Wu et al. reported that a Wrec of 0.22 J/cm3 and a η of 90% could be obtained at 47 kV/cm in BaTiO3@SrTiO3 ceramic.35 Huang et al. found that the 95 wt%Ba0.4Sr0.6TiO3-5 wt%MgO ceramic showed a Wrec of 1.50 J/cm3 and a η of 88.5% at 300 kV/cm using spark plasma sintering.36 Cui et al. reported that a Wrec of 1.70 J/cm3 at 210 kV/cm can be obtained in binary SrTiO3-Bi0.5Na0.5TiO3 ceramics.37 However, according to the previous reports of ST-based ceramics, the η is higher than 80% while the Wrec is less than 2 J/cm3 because of small Pmax. Thus, it is urgent to improve the Pmax and Wrec of ST-based ceramics for energy storage applications. In order to obtain high Wrec and high η at the same time, we adopted composition control to enhance the Pmax of ST-based lead-free ceramics in this work. Novel (1-x)SrTiO3-x(Bi0.5Na0.5TiO3-Ba0.94La0.04Zr0.02Ti0.98O3)

((1-x)ST-x(BNT-BLZT))

lead-free ceramics were selected and fabricated using the tape-casting process and the subsequent conventional solid-state sintering method. Finally, the high Wrec (2.83 J/cm3) and high η (85%) can be simultaneously achieved for 0.8ST-0.2(BNT-BLZT) ceramic. The significantly enhanced Wrec (2.83 J/cm3) is almost 2 times higher than previous reported results of lead-free ceramics with η > 80%. Therefore, the (1-x)ST-x(BNT-BLZT) (x = 0-0.5) ceramics can be used for high energy storage applications.

ACS Paragon Plus Environment

Page 6 of 31

Page 7 of 31

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Sustainable Chemistry & Engineering

EXPERIMENTAL SECTION Materials Preparation. The (1-x)ST-x(BNT-BLZT) (x = 0.0-0.5) lead-free ceramics were fabricated using the tape-casting process and sintered by solid-state sintering method. Firstly, ST and BNT-BLZT powders were synthesized, respectively. SrCO3 (>99.0%) and TiO2 (>99.8%) were weighed by the nominal composition of ST and ball milled in alcohol for 12 h. The obtained powders were dried and calcined at 1150 oC for 4 h in air, and then milled again in alcohol for 12 h. Bi2O3 (> 99%), Na2CO3 (> 99.8%), TiO2 (>99.8%), BaCO3 (>99.0%), La2O3 (> 99.9%) and ZrO2 (> 99%) were the raw materials of BNT-BLZT. The preparation process was as same as that of ST powder, except that BNT-BLZT powders were calcined at 800 oC for 4 h. BNT-BLZT and ST powders were mixed according to the composition of (1-x)ST-x(BNT-BLZT) and ball-milled in alcohol for 12 h. After drying, the (1-x)ST-x(BNT-BLZT) mixture powders can be obtained. In order to get the slurries, dispersant (glycerol trioleate) and solvent (alcohol and butanone) were milled for 4 h. Then some plasticizer (dibutyl phthalate), binder (polyvinyl butyral and polyethylene glycol) and (1-x)ST-x(BNT-BLZT) powders were added and milled for 4 h again. Finally, the obtained slurries were casted on Mylar substrates. The schematic drawing of the fabrication process are shown in Figure 2. The ceramic membrane was laminated first and uniaxially pressed under 120 MPa at room temperature. And then, heating at 80 °C and pressing under 200 MPa again. Finally, binders were removed at 550 oC for 24 h and all samples were sintered at 1300-1350 oC for 2 h. To prevent the

ACS Paragon Plus Environment

ACS Sustainable Chemistry & Engineering

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

loss of volatile Bi3+ and Na+, the samples were embedded in the corresponding powders during sintering.

Figure 2 Schematic drawing of the fabrication process for (1-x)ST-x(BNT-BLZT) ceramics.

Characterization. The X-ray diffractometer (XRD, D-MAX 2200pc, Rigaku Co., Tokyo, Japan) was used to detect phase structure of (1-x)ST-x(BNT-BLZT) ceramics. The microstructure of (1-x)ST-x(BNT-BLZT) ceramics was observed by a scanning electron microscopy (SEM, S4800, Rigaku Co., Japan). The frequency dependent dielectric properties were measured by an impedance analyzer (E4990A, Agilent, Palo Alto, CA). The temperature dependent dielectric properties were measured using an LCR meter (3532-50, Hioki, Ueda, Japan) at a frequency of 1 kHz. The P-E loops were measured by a ferroelectric test system (Premier II, Radiant, USA) and the samples with a thickness of 0.20 mm. RESULTS AND DISCUSSION

ACS Paragon Plus Environment

Page 8 of 31

Page 9 of 31

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Sustainable Chemistry & Engineering

Figure 3 shows the XRD results of (1-x)ST-x(BNT-BLZT) ceramics. It can be found that a stable single perovskite phase can be formed for (1-x)ST-x(BNT-BLZT) ceramics and no any secondary phase can be detected. It exhibits that BNT-BLZT and ST form a stable perovskite solid solution.

Figure 3 XRD results of (1-x)ST-x(BNT-BLZT) ceramics.

Figure 4(a)-(f) shows the typical morphology of (1-x)ST-x(BNT-BLZT) ceramics. It can be found that all the (1-x)ST-x(BNT-BLZT) ceramics are densely sintered with a homogeneous grain size and few visible pores appear. The grain size of (1-x)ST-x(BNT-BLZT) ceramics can be increased observably with addition of BNT-BLZT. In order to further identify the average grain size, the grain size distributions can be evaluated by a linear interception method using an analytical software (Nano Measurer), as shown in Figure 5(a)-(f). It can be found that the average grain size increases from 1.09 µm to 4.86 µm with increasing BNT-BLZT content. The increase of grain size might be due to the fact that A-site elements ( Bi3+

ACS Paragon Plus Environment

ACS Sustainable Chemistry & Engineering

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

and Na+) volatilize inevitably due to their low melting points,22, 38 leading to the presence of oxygen vacancies and promoting mass transportation during sintering.39

Figure 4 SEM of (1-x)ST-x(BNT-BLZT) ceramics: (a) x = 0; (b) x = 0.1; (c) x = 0.2; (d) x = 0.3; (e) x = 0.4; (f) x = 0.5.

Figure 5 Grain size distributions of (1-x)ST-x(BNT-BLZT) ceramics.

ACS Paragon Plus Environment

Page 10 of 31

Page 11 of 31

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Sustainable Chemistry & Engineering

Figure 6 Frequency dependent dielectric properties for (1-x)ST-x(BNT-BLZT) ceramics.

Figure 7 Temperature dependent dielectric properties for (1-x)ST-x(BNT-BLZT) ceramics at 1 kHz.

Figure 6 shows the frequency dependent dielectric constant (εʹ) and dielectric loss (tanδ) for (1-x)ST-x(BNT-BLZT) ceramics. It can be found that the εʹ almost remains a constant with measurement frequency when x ≤ 0.4, and then an excellent frequency stability of εʹ can be observed. In addition, the εʹ of (1-x)ST-x(BNT-BLZT) ceramics increases with increasing BNT-BLZT content gradually. It is due to the fact that compared with ST, BNT-BLZT has larger εʹ and higher Curie temperature (TC).23,

ACS Paragon Plus Environment

ACS Sustainable Chemistry & Engineering

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

40

Meanwhile, all the samples keep a low value of tanδ (< 0.05, at 1 kHz). It is

conducive to small energy loss.41

Figure 8(a) P-E loops of (1-x)ST-x(BNT-BLZT) ceramics at 10 Hz; (b) Variation of Pr, Pmax and Pmax - Pr under 160 kV/cm estimated from P-E loops for (1-x)ST-x(BNT-BLZT) ceramics.

Figure 7 shows the temperature (-180 oC to 150 oC) dependent εʹ and tanδ for (1-x)ST-x(BNT-BLZT) ceramics. No dielectric peak can be found when x = 0, which is due to the fact that pure ST has low value of TC. Only one dielectric peak can be found for (1-x)ST-x(BNT-BLZT) ceramics at measured temperature range and the temperature of maximum dielectric constant (Tm) shifts towards higher temperatures from -121 oC to 16 oC with increasing the value of x from 0.1 to 0.5. Moreover, the

ACS Paragon Plus Environment

Page 12 of 31

Page 13 of 31

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Sustainable Chemistry & Engineering

maximum value of εʹ increases from 2617 to 4541 for (1-x)ST-x(BNT-BLZT) ceramics with increasing the value of x from 0.1 to 0.5. Meanwhile, as shown in Figure 7, the phase transition temperature range around Tm becomes broader and broader with increasing BNT-BLZT content. This is a typical characteristic of the relaxor ferroelectric ceramics and beneficial to obtain high Wrec due to very small Pr.42 Moreover, it can be found that the tanδ is less than 0.04 at -50-150 oC when x ≤ 0.3, which is conducive to small energy loss.41

Figure 9(a) Weibull distribution of (1-x)ST-x(BNT-BLZT) ceramics; (b) BDS as a function of different composition.

Figure 8(a) shows the P-E loops of (1-x)ST-x(BNT-BLZT) ceramics at 10 Hz and 160 kV/cm. As shown in Figure 8(a), the P-E loops transform from a linear

ACS Paragon Plus Environment

ACS Sustainable Chemistry & Engineering

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

dielectric for pure ST ceramic to a relaxor ferroelectric with increasing BNT-BLZT content gradually. This phenomenon indicates that the ferroelectric properties of (1-x)ST-x(BNT-BLZT) ceramics can be improved with increasing BNT-BLZT content. That is to say, Pmax and Pr increase substantially with increasing BNT-BLZT content, as shown in Figure 8(b). The Pmax increases gradually and reaches the maximum value of 28.44 µC/cm2 for the sample of x = 0.5 at 160 kV/cm, which is 4.44 times as large as that of pure ST (6.40 µC/cm2). In addition, a slow and slight increase in Pr can be found with increasing BNT-BLZT content gradually. Thus, the Pmax - Pr increases gradually upon increasing BNT-BLZT content. The significant improvement of Pmax and Pmax - Pr would be definitely beneficial to enhance the energy storage density.

Figure 10 P-E loops of (1-x)ST-x(BNT-BLZT) ceramics at critical electric field.

For advanced pulsed power capacitor application, high value of BDS is an important characteristic. Weibull distribution is usually used for BDS analysis due to its statistical nature of failure.32, 43, 44 Figure 9(a) shows the characteristic breakdown

ACS Paragon Plus Environment

Page 14 of 31

Page 15 of 31

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Sustainable Chemistry & Engineering

strength of (1-x)ST-x(BNT-BLZT) ceramics analyzed by a Weibull distribution. The plot is described as shown in the following equations.9, 35, 45          1

(4) 

"#$

%

(5)

Figure 11(a) Calculated W and Wrec with different values of x; (b) Calculated Wloss and η with different values of x.

Where Ei is breakdown voltage of each sample, i is serial number of samples and n is the total number of samples. The order of Ei is arranged as follow. $ & ' & ( ⋯ &  & ⋯ & "

(6)

Figure 9(a) shows that all data can be fitted well with Weibull distribution and the shape parameter β was found between 13.42 and 23.06. The values of BDS for (1-x)ST-x(BNT-BLZT) ceramics are obtained and shown in Figure 9(b). It can be

ACS Paragon Plus Environment

ACS Sustainable Chemistry & Engineering

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

found that the BDS values decrease gradually with increasing BNT-BLZT content, which may be due to the fact that increasing of grain size. In general, small and homogeneous grain size is beneficial to obtain high BDS.16, 46

Figure 12(a) Unipolar P-E loops of 0.8ST-0.2(BNT-BLZT) ceramics with different electric fields at room temperature; (b) Calculated W and Wrec from (a); (c) Calculated Wloss and η from (a).

Figure 10 shows the P-E loops of (1-x)ST-x(BNT-BLZT) ceramics at 10 Hz and critical electric field. All the samples display slim P-E loops, high BDS, and large

ACS Paragon Plus Environment

Page 16 of 31

Page 17 of 31

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Sustainable Chemistry & Engineering

Pmax. According to Equation (2), (1-x)ST-x(BNT-BLZT) ceramics are favorable for obtaining high Wrec due to the fact that they simultaneously possess large Pmax, small Pr, and high BDS. The electric energy storage behaviors of (1-x)ST-x(BNT-BLZT) ceramics were calculated using P-E loops, as shown Figure 11. Both W and Wrec increase firstly and then decrease with increasing BNT-BLZT content, and reach the maximum values (W and Wrec is 3.33 J/cm3 and 2.83 J/cm3, respectively) with the composition of 0.8ST-0.2(BNT-BLZT). For the practical application, as the lead-free dielectric ceramic materials for advanced pulsed power energy storage capacitors, not only high Wrec but also high η is desirable.47 Because dielectric materials with lower η lose a higher amount of their stored energy to heat, which heat would degrade the properties of the dielectric material. Therefore, it is very important to obtain high η and low Wloss. Figure 11(b) shows the value of η and Wloss for (1-x)ST-x(BNT-BLZT) ceramics with different values of x. It can be found that Wloss shows an increment trend while η shows a decrement trend with increasing BNT-BLZT content, and the values of η are more than 80% for (1-x)ST-x(BNT-BLZT) ceramics when x ≤ 0.4. Figure 12(a) demonstrates the unipolar P-E loops with different electric fields at room temperature for 0.8ST-0.2(BNT-BLZT) ceramic. The value of Pmax increases from 13.39 µC/cm2 to 23.85 µC/cm2 with increasing the electric fields from 120 kV/ cm to 320 kV/cm. Therefore, a much higher Wrec can be achieved by enhancing the value of BDS for 0.8ST-0.2(BNT-BLZT) ceramic. Figure 12(b) and (c) show the energy storage properties of 0.8ST-0.2(BNT-BLZT) ceramic with different electric

ACS Paragon Plus Environment

ACS Sustainable Chemistry & Engineering

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

fields at room temperature. The results show that W and Wrec increase from 0.73 J/cm3 and 0.69 J/cm3 to 3.33 J/cm3 and 2.83 J/cm3, respectively, with increasing the electric field from 120 kV/cm to 320 kV/cm. But the value of η decreases with increasing the electric field, which is attributed to the fact that Wloss increases with increasing the electric field.16 The (1-x)ST-x(BNT-BLZT) ceramic exhibits the highest W ( 3.33 J/cm3), Wrec (2.83 J/cm3) and a high η of 85% at 320 kV/cm.

Figure 13 A comparison of η and Wrec between (1-x)ST-x(BNT-BLZT) ceramics and other lead-free ceramics.

For further evaluating the energy storage properties of (1-x)ST-x(BNT-BLZT) ceramics, a comparison of Wrec and η for (1-x)ST-x(BNT-BLZT) ceramics and other lead-free ceramics were surveyed in Figure 13.9, 11, 21, 22, 24, 35, 36, 42, 48-62 It can be found that the values of Wrec are less than 1.5 J/cm3 for most of lead-free ceramics. KNN-based lead-free ceramics possess high Wrec (~ 4 J/cm3) while their values of η are lower than 65%. The values of η are higher than 80% for ST-based lead-free ceramics, but the values of Wrec are less than 2 J/cm3. In this study, high Wrec (2.83

ACS Paragon Plus Environment

Page 18 of 31

Page 19 of 31

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Sustainable Chemistry & Engineering

J/cm3) and high η (85%) can be achieved simultaneously for 0.8ST-0.2(BNT-BLZT) ceramic. It can be observed from Figure 13 that the significantly enhanced Wrec (2.83 J/cm3) is almost 2 times higher than previous reported results of lead-free ceramics with η > 80%. CONCLUSIONS In this study, novel ST-BNT-BLZT lead-free ceramics were successfully fabricated by the tape-casting process and sintered via solid-state sintering method for achieving large Pmax, high BDS, high Wrec and high η. All the samples have slim P-E loops. The Pmax gradually increases and reaches the maximum value of 28.44 µC/cm2 for the sample with x = 0.5 at 160 kV/cm, which is 4.44 times as large as that of pure ST (6.40 µC/cm2). A high Wrec (2.83 J/cm3) and high η (85%) can be simultaneously achieved for 0.8ST-0.2(BNT-BLZT) ceramic at 320 kV/cm. The significantly enhanced Wrec (2.83 J/cm3) is almost 2 times higher than previous reported results of lead-free ceramics with η > 80%, which indicates that the (1-x)ST-x(BNT-BLZT) ceramics can be considered as potential candidate ceramic capacitors for high energy storage applications. In addition, the finding in this study could push the development of ST-based ceramics with enhanced Pmax, high Wrec and high η in the future. ACKNOWLEDGMENTS This work is supported by the National Natural Science Foundation of China (Grant No. 51572159, 51702196), the Chinese Postdoctoral Science Foundation (Grant No. 2016M590916), the Science and Technology Foundation of Weiyang

ACS Paragon Plus Environment

ACS Sustainable Chemistry & Engineering

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

District of Xi’an City (Grant No. 201605), the Industrialization Foundation of Education Department of Shaanxi Provincial Government (Grant No. 16JF002). REFERENCES (1) Dang, Z. M.; Yuan, J. K.; Zha, J. W.; Zhou, T.; Li, S. T.; Hu, G. H. Fundamentals, processes and applications of high-permittivity polymer-matrix composites. Prog. Mater. Sci. 2012, 57, 660-723. DOI: 10.1016/j.pmatsci.2011.08.001. (2) Zhao, Y.; Hao, X.; Zhang, Q. Energy-storage properties and electrocaloric effect of Pb(1-3x/2)LaxZr0.85Ti0.15O3 Antiferroelectric Thick Films. ACS Appl. Mater. Interfaces 2014, 6, 11633-11639. DOI: 10.1021/am502415z. (3) Park, M. H.; Kim, H. J.; Kim, Y. J.; Moon, T.; Kim, K. D.; Hwang, C. S. Thin HfxZr1-xO2 films: A new lead-free system for electrostatic supercapacitors with large energy storage density and robust thermal stability. Adv. Energy Mater. 2014, 4, 1400610. DOI: 10.1002/aenm.201400610. (4) Chu, B. J.; Zhou, X.; Ren, K. L.; Neese, B.; Li, M. R.; Wang, Q.; Bauer, F.; Zhang, Q. M. A dielectric polymer with high electric energy density and fast discharge speed. Science 2006, 313, 334-336. DOI: 10.1126/science.1127798. (5) Khanchaitit, P.; Han, K.; Gadinski, M. R.; Li, Q.; Wang, Q. Ferroelectric polymer networks with high energy density and improved discharged efficiency for dielectric energy storage. Nat. Commun. 2013, 4, 1-7. DOI: 10.1038/ncomms3845. (6) Hao, X. A review on the dielectric materials for high energy-storage application. J. Adv. Dielect. 2013, 03, 1330001. DOI: 10.1142/S2010135X13300016.

ACS Paragon Plus Environment

Page 20 of 31

Page 21 of 31

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Sustainable Chemistry & Engineering

(7) Yao, K.; Chen, S.; Rahimabady, M.; Mirshekarloo, M. S.; Yu, S.; Tay, F.; Sritharan, T.; Lu, L. Nonlinear dielectric thin films for high power electric storage with energy density comparable with electrochemical supercapacitors. IEEE Trans. Ultrason. Ferr. 2011, 58, 1968-1974. DOI: 10.1109/TUFFC.2011.2039. (8) Qu, B.; Du, H.; Yang, Z. Lead free relaxor ferroelectric ceramics with high optical transparency and energy storage ability. J. Mater. Chem. C 2016, 4, 1795-1803. DOI: 10.1039/c5tc04005a. (9) Yang, H.; Yan, F.; Lin, Y.; Wang, T.; Wang, F.; Wang, Y.; Guo, L.; Tai, W.; Wei, H. Lead-free BaTiO3-Bi0.5Na0.5TiO3-Na0.73Bi0.09NbO3 relaxor ferroelectric ceramics for high energy storage. J. Eur. Ceram. Soc. 2017, 37, 3303-3311. DOI: 10.1016/j.jeurceramsoc.2017.03.071. (10) Liu, G.; Fan, H.; Dong, G.; Shi, J.; Chang, Q. Enhanced energy storage and dielectric

properties

of

Bi0.487Na0.427K0.06Ba0.026TiO3-xCeO2

anti-ferroelectric

ceramics. J. Alloy. Compd. 2016, 664, 632-638. DOI: 10.1016/j.jallcom.2015.12.260. (11) Xie, J.; Hao, H.; Liu, H.; Yao, Z.; Song, Z.; Zhang, L.; Xu, Q.; Dai, J.; Cao, M. Dielectric relaxation behavior and energy storage properties of Sn modified SrTiO3 based

ceramics.

Ceram.

Int.

2016,

42,

12796-12801.

DOI:

10.1016/j.ceramint.2016.05.042. (12) Zhang, G.; Liu, S.; Yu, Y.; Zeng, Y.; Zhang, Y.; Hu, X.; Jiang, S. Microstructure and electrical properties of (Pb0.87Ba0.1La0.02)(Zr0.68Sn0.24Ti0.08)O3 anti-ferroelectric

ACS Paragon Plus Environment

ACS Sustainable Chemistry & Engineering

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 22 of 31

ceramics fabricated by the hot-press sintering method. J. Eur. Ceram. Soc. 2013, 33, 113-121. DOI: 10.1016/j.jeurceramsoc.2012.08.011. (13) Zhang, L.; Jiang, S.; Zeng, Y.; Fu, M.; Han, K.; Li, Q.; Wang, Q.; Zhang, G. Y doping and grain size co-effects on the electrical energy storage performance of (Pb0.87Ba0.1La0.02)(Zr0.65Sn0.3Ti0.05)O3 anti-ferroelectric ceramics. Ceram. Int. 2014, 40, 5455-5460. DOI: 10.1016/j.ceramint.2013.10.131. (14) Xu, L.; He, C.; Yang, X.; Wang, Z.; Li, X.; Tailor, H. N.; Long, X. Composition dependent

structure,

dielectric

and

energy

storage

properties

of

Pb(Tm1/2Nb1/2)O3-Pb(Mg1/3Nb2/3)O3 antiferroelectric ceramics. J. Eur. Ceram. Soc. 2017, 37, 3329-3334. DOI: 10.1016/j.jeurceramsoc.2017.04.005. (15) Rödel, J.; Jo, W.; Seifert, K.; Anton, E.; Granzow, T.; Damjanovic, D. Perspective on the development of lead-free piezoceramics. J. Am. Ceram. Soc. 2009, 92, 1153-1177. DOI: 10.1111/j.1551-2916.2009.03061.x. (16) Wang, T.; Jin, L.; Li, C.; Hu, Q.; Wei, X. Relaxor ferroelectric BaTiO3-Bi(Mg2/3Nb1/3)O3 ceramics for energy storage application. J. Am. Ceram. Soc. 2015, 98, 559-566. DOI: 10.1111/jace.13325. (17) Yao, M.; Pu, Y.; Zhang, L.; Chen, M. Enhanced energy storage properties of (1-x)Bi0.5Na0.5TiO3-xBa0.85Ca0.15Ti0.9Zr0.1O3 ceramics. Mater. Lett. 2016, 174, 110-113. DOI: 10.1016/j.matlet.2016.03.089. (18) Chao, S.; Dogan, F. BaTiO3-SrTiO3 layered dielectrics for energy storage. Mater. Lett. 2011, 65, 978-981. DOI: 10.1016/j.matlet.2010.12.043.

ACS Paragon Plus Environment

Page 23 of 31

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Sustainable Chemistry & Engineering

(19) Yang, H.; Yan, F.; Zhang, G.; Lin, Y.; Wang, F. Dielectric behavior and impedance

spectroscopy

of

lead-free

Ba0.85Ca0.15Zr0.1Ti0.9O3

ceramics

with

B2O3-Al2O3-SiO2 glass-ceramics addition for enhanced energy storage. J. Alloy. Compd. 2017, 720, 116-125. DOI: 10.1016/j.jallcom.2017.05.158. (20) Xu, Q.; Xie, J.; He, Z.; Zhang, L.; Cao, M.; Huang, X.; Lanagan, M.; Hao, H.; Yao, Z.; Liu, H. Energy-storage properties of Bi0.5Na0.5TiO3-BaTiO3-KNbO3 ceramics fabricated by wet-chemical method. J. Eur. Ceram. Soc. 2017, 37, 99-106. DOI: 10.1016/j.jeurceramsoc.2016.07.011. (21) Shen, Z.; Wang, X.; Luo, B.; Li, L. BaTiO3-BiYbO3 perovskite materials for energy storage applications. J. Mater. Chem. A 2015, 3, 18146-18153. DOI: 10.1039/c5ta03614c. (22) Xu, Q.; Liu, H.; Zhang, L.; Xie, J.; Hao, H.; Cao, M.; Yao, Z.; Lanagan, M. Structure and electrical properties of lead-free Bi0.5Na0.5TiO3-based ceramics for energy-storage

applications.

RSC

Adv.

2016,

6,

59280-59291.

DOI:

10.1039/c6ra11744a. (23) Wang, Y.; Lv, Z.; Xie, H.; Cao, J. High energy-storage properties of [(Bi1/2Na1/2)0.94 Ba0.06]La(1-x)ZrxTiO3 lead-free anti-ferroelectric ceramics. Ceram. Int. 2014, 40, 4323-4326. DOI: 10.1016/j.ceramint.2013.08.099. (24) Yang, Z.; Du, H.; Qu, S.; Hou, Y.; Ma, H.; Wang, J.; Wang, J.; Wei, X.; Xu, Z. Significantly enhanced recoverable energy storage density in potassium-sodium

ACS Paragon Plus Environment

ACS Sustainable Chemistry & Engineering

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 24 of 31

niobate-based lead free ceramics. J. Mater. Chem. A 2016, 4, 13778-13785. DOI: 10.1039/c6ta04107h. (25) Jo, H. R.; Lynch, C. S. A high energy density relaxor antiferroelectric pulsed capacitor dielectric. J. Appl. Phys. 2016, 119, 024104. DOI: 10.1063/1.4939617. (26) Wang, K.; Li, J. (K, Na)NbO3-based lead-free piezoceramics: Phase transition, sintering and property enhancement. J. Adv. Ceram. 2012, 1, 24-37. DOI: 10.1007/s40145-012-0003-3. (27) Ibn-Mohammed, T.; S. Koh, I. Reaney; Sinclair, D.; Mustapha, K.; Acquaye, A.; Wang, D. Are lead-free piezoelectrics more environmentally friendly? MRS Commun. 2017, 7, 1-7. DOI: 10.1557/mrc.2017.10. (28) Malič, B.; Koruza, J.; Hreščak, J.; Bernard, J.; Wang, K.; Fisher, J.; Benčan, A. Sintering of lead-free piezoelectric sodium potassium niobate ceramics. Materials 2015, 8, 8117-8146. DOI: 10.3390/ma8125449. (29) Xiong, Z.; Zhou, X.; Zen, W.; Baba-Kishi, K.; Chen, S. Development of ferroelectric ceramics with high dielectric constant and low dissipation factor for high-voltage

capacitors.

J.

Electroceram.

1999,

3,

239-244.

DOI:

10.1023/A:1009925416878. (30) Wang, Z.; Cao, M.; Yao, Z.; Song, Z.; Li, G.; Hu, W.; Hao, H.; Liu, H. Dielectric relaxation behavior and energy storage properties in SrTiO3 ceramics with trace amounts

of

ZrO2

additives.

Ceram.

Int.

2014,

40,

10.1016/j.ceramint.2014.05.147.

ACS Paragon Plus Environment

14127-14132.

DOI:

Page 25 of 31

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Sustainable Chemistry & Engineering

(31) Zhang, G.; Liu, H.; Yao, Z.; Cao, M.; Hao, H. Effects of Ca doping on the energy storage properties of (Sr, Ca)TiO3 paraelectric ceramics. J. Mater. Sci: Mater. El. 2015, 26, 2726-2732. DOI: 10.1007/s10854-015-2749-1. (32) Song, Z.; Zhang, S.; Liu, H.; Hao, H.; Cao, M.; Li, Q.; Wang, Q.; Yao, Z.; Wang, Z.; Lanagan, M. Improved energy storage properties accompanied by enhanced interface polarization in annealed microwave-sintered BST. J. Am. Ceram. Soc. 2015, 98, 3212-3222. DOI: 10.1111/jace.13741. (33) Correia, T. M.; Millen, M. M.; Rokosz, M. K.; Weaver, P. M.; Gregg, J. M.; Viola, G.; Cain, M. G. A lead-free and high-energy density ceramic for energy storage applications. J. Am. Ceram. Soc. 2013, 96, 2699-2702. DOI: 10.1111/jace.12508. (34) Wang, T.; Jin, L.; Shu, L.; Hu, Q.; Wei, X. Energy storage properties in Ba0.4Sr0.6TiO3

ceramics

with

addition

of

semi-conductive

BaO-B2O3-SiO2-Na2CO3-K2CO3 glass. J. Alloy. Compd. 2014, 617, 399-403. DOI: 10.1016/j.jallcom.2014.08.038. (35) Wu, L.; Wang, X.; Gong, H.; Hao, Y.; Shen, Z.; Li, L. Core-satellite BaTiO3@SrTiO3 assemblies for a local compositionally graded relaxor ferroelectric capacitor with enhanced energy storage density and high energy efficiency. J. Mater. Chem. C 2015, 3, 750-758. DOI: 10.1039/c4tc02291b. (36) Huang, Y.; Wu, Y.; Qiu, W.; Li, J.; Chen, X. Enhanced energy storage density of Ba0.4Sr0.6TiO3-MgO composite prepared by spark plasma sintering. J. Eur. Ceram. Soc. 2015, 35, 1469-1476. DOI: 10.1016/j.jeurceramsoc.2014.11.022.

ACS Paragon Plus Environment

ACS Sustainable Chemistry & Engineering

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 26 of 31

(37) Cui, C.; Pu, Y.; Gao, Z.; Wan, J.; Guo, Y.; Hui, C.; Wang, Y.; Cui, Y. Structure, dielectric and relaxor properties in lead-free ST-NBT ceramics for high energy storage

applications.

J.

Alloy.

Compd.

711,

2017,

319-326.

DOI:

10.1016/j.jallcom.2017.04.023. (38) Zhu, M.; Hu, H.; Lei, N.; Hou, Y.; Yan, H. Dependence of depolarization temperature

on

cation

vacancies

and

lattice

distortion

for

lead-free

74Bi1/2Na1/2TiO3-20.8Bi1/2K1/2TiO3-5.2BaTiO3 ferroelectric ceramics. Appl. Phys. Lett. 2009, 94, 182901. DOI: 10.1063/1.3130736. (39) Xu, Q.; Chen, M.; Chen, W.; Liu, H.; Kim, B.; Ahn, B. Effect of CoO additive on structure and electrical properties of (Na0.5Bi0.5)0.93Ba0.07TiO3 ceramics prepared by the

citrate

method.

Acta

Mater.

2008,

56,

642-650.

DOI:

10.1016/j.actamat.2007.10.014. (40) Jin, C. C.; Wang, F. F.; Yao, Q. R.; Tang, Y. X.; Wang, T.; Shi, W. Z. Ferroelectric, dielectric properties and large strain response in Zr-modified (Bi0.5Na0.5)TiO3-BaTiO3 lead-free ceramics. Ceram. Int. 2014, 40, 6143-6150. DOI: 10.1016/j.ceramint.2013.11.066. (41) Wang, Y.; Cui, J.; Yuan, Q.; Niu, Y.; Bai, Y.; Wang, H. Significantly enhanced breakdown strength and energy density in sandwich-structured barium titanate/ poly(vinylidene fluoride) nanocomposites. Adv. Mater. 2015, 27, 6658-6663. DOI: 10.1002/adma.201503186.

ACS Paragon Plus Environment

Page 27 of 31

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Sustainable Chemistry & Engineering

(42) Shao, T.; Du, H.; Ma, H.; Qu, S.; Wang, J.; Wang, J.; Wei, X.; Xu, Z. Potassium-sodium niobate based lead-free ceramics: novel electrical energy storage materials. J. Mater. Chem. A 2017, 5, 554-563. DOI: 10.1039/c6ta07803f. (43) Tuncer, E.; James, D. R.; Sauers, I.; Ellis, A. R.; Pace, M. O. On dielectric breakdown statistics. J. Phys. D Appl. Phys. 2006, 39, 4257-4268. DOI: 10.1088/0022-3727/39/19/020. (44) Su, X.; Riggs, B. C.; Tomozawa, M.; Nelson, J. K.; Chrisey, D. B. Preparation of BaTiO3/low melting glass core-shell nanoparticles for energy storage capacitor applications. J. Mater. Chem. A 2014, 2, 18087-18096. DOI: 10.1039/c4ta04282d. (45) Huang, J.; Zhang, Y.; Ma, T.; Li, H.; Zhang, L. Correlation between dielectric breakdown strength and interface polarization in barium strontium titanate glass ceramics. Appl. Phys. Lett. 2010, 96, 042902. DOI: 10.1063/1.3293456. (46) Li, Y.; Liu, H.; Z.Yao; Xu, J.; Cui, Y.; Hao, H.; Cao, M.; Yu, Z. Characterization and energy storage density of BaTiO3-Ba(Mg1/3Nb2/3)O3 ceramics. Mater. Sci. Forum 2010, 654, 2045-2048. DOI: 10.4028/www.scientific.net/MSF.654-656.2045. (47) Wang, H.; Liu, J.; Zhai, J.; Shen, B. Ultra high energy-storage density in the barium potassium niobate-based glass-ceramics for energy-storage applications. J. Am. Ceram. Soc. 2016, 99, 2909-2912. DOI: 10.1111/jace.14446. (48) Yang, H.; Yan, F.; Lin, Y.; Wang, T.; He, L.; Wang, F. A lead free relaxation and high energy storage efficiency ceramics for energy storage applications. J. Alloy. Compd. 2017, 710, 436-445. DOI: 10.1016/j.jallcom.2017.03.261.

ACS Paragon Plus Environment

ACS Sustainable Chemistry & Engineering

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

Page 28 of 31

(49) Li, W.; Zhou, D.; Pang, L. Structure and energy storage properties of Mn-doped (Ba,Sr)TiO3-MgO composite ceramics. J. Mater. Sci. Mater. El. 2017, 28, 8749-8754. DOI: 10.1007/s10854-017-6600-8. (50) Ye, X.; Li, Y.; Bian, J. Dielectric and energy storage properties of Mn-doped Ba0.3Sr0.475La0.12Ce0.03TiO3 dielectric ceramics. J. Eur. Ceram. Soc. 2017, 37, 107-114. DOI: 10.1016/j.jeurceramsoc.2016.08.002. (51) Li, L.; Yu, X.; Cai, H.; Liao, Q.; Han, Y.; Gao, Z. Preparation and dielectric properties of BaCu(B2O5)-doped SrTiO3-based ceramics for energy storage. Mater. Sci. Eng. B 2013, 178, 1509-1514. DOI: 10.1016/j.mseb.2013.08.016. (52) Puli, V. S.; Pradhan, D. K.; Chrisey, D. B.; Tomozawa, M.; Sharma, G. L.; Scott, J. F.; Katiyar, R. S. Structure, dielectric, ferroelectric, and energy density properties of (1-x)BZT-xBCT ceramic capacitors for energy storage applications. J. Mater. Sci. 2013, 48, 2151-2157. DOI: 10.1007/s10853-012-6990-1. (53) Xu, Q.; Liu, H.; Song, Z.; Huang, X.; Ullah, A.; Zhang, L.; Xie, J.; Hao, H.; Cao, M.; Yao, Z. A new energy-storage ceramic system based on Bi0.5Na0.5TiO3 ternary solid

solution.

J.

Mater.

Sci.

Mater.

El.

2016,

27,

322-329.

DOI:

10.1007/s10854-015-3757-x. (54) Li, Q.; Wang, J.; Liu, Z.; Dong, G.; Fan, H. Enhanced energy-storage properties of BaZrO3-modified 0.80Bi0.5Na0.5TiO3-0.20Bi0.5K0.5TiO3 lead-free ferroelectric ceramics. J. Mater. Sci. 2016, 51, 1153-1160. DOI: 10.1007/s10853-015-9446-6.

ACS Paragon Plus Environment

Page 29 of 31

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Sustainable Chemistry & Engineering

(55) Xu, Q.; Li, T.; Hao, H.; Zhang, S.; Wang, Z.; Cao, M.; Yao, Z.; Liu, H. Enhanced energy storage properties of NaNbO3 modified Bi0.5Na0.5TiO3 based ceramics. J. Eur. Ceram. Soc. 2015, 35, 545-553. DOI: 10.1016/j.jeurceramsoc.2014.09.003. (56) Liu, X.; Du, H.; Liu, X.; Shi, J.; Fan, H. Energy storage properties of BiTi0.5Zn0.5O3-Bi0.5Na0.5TiO3-BaTiO3 relaxor ferroelectrics. Ceram. Int. 2016, 42, 17876-17879. DOI: 10.1016/j.ceramint.2016.08.087. (57) Pu, Y.; Yao, M.; Zhang, L.; Jing, P. High energy storage density of 0.55Bi0.5Na0.5TiO3-0.45Ba0.85Ca0.15Ti0.9-xZr0.1SnxO3 ceramics. J. Alloy. Compd. 2016, 687, 689-695. DOI: 10.1016/j.jallcom.2016.06.181. (58) Wu, L.; Wang, X.; Li, L. Lead-free BaTiO3-Bi(Zn2/3Nb1/3)O3 weakly coupled relaxor ferroelectric materials for energy storage. RSC Adv. 2016, 6, 14273-14282. DOI: 10.1039/C5RA21261H. (59) Zheng, D.; Zuo, R.; Zhang, D.; Li, Y. Novel BiFeO3-BaTiO3-Ba(Mg1/3Nb2/3)O3 lead-free relaxor ferroelectric ceramics for energy-storage capacitors. J. Am. Ceram. Soc. 2015, 98, 2692-2695. DOI: 10.1111/jace.13737. (60) Cao, W.; Li, W.; Dai, X.; Zhang, T.; Sheng, J.; Hou, Y.; Fei, W. Large electrocaloric response and high energy-storage properties over a broad temperature range in lead-free NBT-ST ceramics. J. Eur. Ceram. Soc. 2016, 36, 593-600. DOI: 10.1016/j.jeurceramsoc.2015.10.019. (61)

Zheng,

D.;

Zuo,

R.

Enhanced

energy

storage

properties

in

La(Mg1/2Ti1/2)O3-modified BiFeO3-BaTiO3 lead-free relaxor ferroelectric ceramics

ACS Paragon Plus Environment

ACS Sustainable Chemistry & Engineering

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

within a wide temperature range. J. Eur. Ceram. Soc. 2017, 37, 413-418. DOI: 10.1016/j.jeurceramsoc.2016.08.021. (62) Cao, W.; Li, W.; Zhang, T.; Sheng, J.; Hou, Y.; Feng, Y.; Yu, Y.; Fei, W. High-energy storage density and efficiency of (1-x)[0.94NBT-0.06BT]-xST lead-free ceramics. Energy Technol. 2015, 3, 1198-1204. DOI: 10.1002/ente.201500173.

ACS Paragon Plus Environment

Page 30 of 31

Page 31 of 31

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60

ACS Sustainable Chemistry & Engineering

For Table of Contents Use Only

Novel

ST-based

lead-free

ceramics

can

be

successfully

fabricated

with

environmentally friendly raw materials and are promising candidate materials for recoverable energy storage.

ACS Paragon Plus Environment