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

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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

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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


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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


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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.


(2) (3)


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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


al.

obtained

the

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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



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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.


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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



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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


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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+



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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.


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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,



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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


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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



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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


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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



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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


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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



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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


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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



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Zheng,

D.;

Zuo,

R.

Enhanced

energy

storage

properties

in

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



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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.


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

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