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Vol. 8. Issue 3.
Pages 2481-3388 (May - June 2019)
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Vol. 8. Issue 3.
Pages 2481-3388 (May - June 2019)
Original Article
DOI: 10.1016/j.jmrt.2019.05.020
Open Access
Superior energy storage performance in Pb0.97La0.02(Zr0.50 Sn0.43Ti0.07)O3 antiferroelectric ceramics
Haojie Xu1, Yu Dan1, Kailun Zou, Guang Chen, Qingfeng Zhang
Corresponding author

Corresponding authors.
, Yinmei Lu, Yunbin He
Corresponding author

Corresponding authors.
Hubei Collaborative Innovation Center for Advanced Organic Chemical Materials, Hubei Key Lab of Ferro & Piezoelectric Materials and Devices, Ministry of Education Key Laboratory of Green Preparation and Application for Functional Materials, School of Materials Science & Engineering, Hubei University, Wuhan 430062, China
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To develop antiferroelectric based dielectric capacitors with superior energy storage capacity, antiferroelectric materials must possess simultaneously large recoverable energy density and high energy efficiency. With this motivation, in this work, we design and prepare Pb0.97La0.02(Zr0.50Sn0.43Ti0.07)O3 antiferroelectric ceramics with high Sn content considering that Sn element can narrow the electric hysteresis loops and thus improve the energy density and efficiency. The experiment results indicate that a large room-temperature recoverable energy density of 3.47J/cm3 and a high energy efficiency of 78% are realized simultaneously in this kind of ceramic. Besides, in the wide temperature range of 20–120°C, the recoverable energy density and the energy efficiency both show superior temperature stability. The large recoverable energy density and high energy efficiency in a wide temperature range demonstrate that the Pb0.97La0.02(Zr0.50Sn0.43Ti0.07)O3 antiferroelectric ceramic is a good candidate for preparing pulse power capacitors usable in various conditions.

High Sn content
Energy storage
Recoverable energy density
Energy efficiency
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Recently, dielectric capacitors have been widely used in aerospace, hybrid vehicles, tank electrothermal guns, and electromagnetic pulse bombs due to their high power density, fast charge/discharge rate (<1μs), long lifetime and low cost [1–4]. With the rapid development of electronic devices toward miniaturization, light weight and integration, it is highly urgent to develop dielectric capacitors with more superior energy storage performance. The key to improving the energy-storage capacity of dielectric capacitors is to prepare dielectric materials capable of holding a large recoverable energy density (Wre) and high energy efficiency (η).

The total energy density (W), Wre, and η of dielectric materials, can be calculated respectively using following equations [5,6]:

where E is the applied electric field, and P, Pr, and Pmax are the spontaneous, remnant, and maximum polarization, respectively. From above equations, it can be seen that in order to obtain large Wre and high η, dielectric materials must have both large Pmax and small Pr. Dielectric materials can be categorized into four groups in terms of the energy storage principle [7,8]. The first is ordinary ferroelectric (FE) materials (such as BaTiO3, PbTiO3, etc.), which have large Pmax, while their Pr is high and thus the η is low. The second and the third are respectively linear dielectric materials (such as glass, Al2O3, etc.) and relaxor FE materials [such as Pb(Mg1/3Nb2/3)O3-PbTiO3, etc.], which have small Pr. However, their Pmax is generally low, resulting in a small Wre. The fourth is antiferroelectric (AFE) materials (such as PbZrO3, (Pb,La)(Zr,Sn,Ti)O3, etc.), which have large Pmax, zero remnant polarization in ideal case, and thus large Wre and high η. Based on these consideration, antiferroelectric materials are the best candidates for developing dielectric capacitors with superior energy storage capacity [7,9,10].

Recently, various types of antiferroelectric materials, especially La modified lead zirconate titanate stannate, have been widely used for preparing dielectric capacitors [11–13]. Previously, much work has been done to improve the energy density of AFE materials. Zhang et al. obtained a large Wre of 4.65J/cm3 in (Pb0.858Ba0.1La0.02Y0.008)(Zr0.65Sn0.3Ti0.05)O3-(Pb0.97La0.02)(Zr0.9Sn0.05Ti0.05)O3 anti-ferroelectric composite ceramics based on large increase of the AFE–FE phase transition electric field. In their following work, via further improvement of the microstructure by spark plasma sintering method, they achieved so far the highest recoverable energy density (∼6.4J/cm3) in bulk ceramics [14,15]. However, for an ideal dielectric capacitor, not only a large Wre is required, but also a high η is desirable, because the lost energy will transform to thermal energy, and thereby leading to a performance deterioration of electronic devices [16]. Compared with other dielectric materials, antiferroelectric materials generally possess both larger Wre and higher η, however, need further enhancement to fulfill practical applications. For example, although Zhang et al. reported a large Wre of 6.4J/cm3, the η was only 62.4% [15]. The low η in AFE materials is mainly attributed to the large difference (ΔE=EFEA) between the AFE–FE phase transition electric field (EF) and FE–AFE phase transition electric field (EA) [16].

Based on above discussions, in order to develop AFE materials with both large Wre and high η, in this work, we design and prepared Pb0.97La0.02(Zr0.50Sn0.43Ti0.07)O3 AFE ceramics with high Sn content, considering that the introduction of the Sn element can narrow down the polarization versus electric field (PE) hysteresis loops and thus leading to the reduction of the ΔE[17]. Besides, we study effects of the electric field and temperature on energy storage properties of the ceramic.

2Experimental procedures

Pb0.97La0.02(Zr0.50Sn0.43Ti0.07)O3 (PLZST) antiferroelectric ceramics were prepared by conventional solid-state reaction method. PbO, La2O3, ZrO2, SnO2, and TiO2 with purity of over 99% were used as starting materials. The powders were weighed according to the stoichiometric formula, ball milled for 4h and then calcined in sealed Al2O3 crucibles at 870°C for 2h. These powders were ball milled again for 8h, dried and pressed into discs (10mm in diameter and 1mm in thickness) using polyvinyl alcohol (PVA) as a binder. After burning off the PVA, the discs were sintered at 1230°C for 2h with a double crucible method. In order to measure electrical properties, the sintered ceramic disks were polished to 0.2mm thickness and then silver paste was fired on both sides of the ceramics at 550°C for 10min.

The crystal structure of the ceramic was characterized by X-ray diffraction (XRD; D8 Advanced, Bruker, Germany). The surface morphology was observed by scanning electron microscopy (SEM; JSM 6510LV, Jeol, Tokyo, Japan). The dielectric properties as a function of the temperature were measured using a TH2827C LCR meter (Tonghui, Changzhou, China) at frequency of 1kHz. The PE hysteresis loops were measured in silicone oil using a ferroelectric test system (PolyK Technologies, USA) combined with a high voltage amplifier (Trek 610E; Trek, Lockport, NY, USA) at the frequency of the 10Hz. Based on the PE hysteresis loops, the energy density and the energy efficiency were calculated.

3Results and discussion

Fig. 1 shows the XRD pattern of the PLZST ceramic. It is obvious that a pure perovskite structure without any second or impure phases can be observed. Besides, as shown in the fine XRD pattern in the 2θ range of 43–45° (inset (a)), the (200) and (002) peaks have an obvious splitting, which demonstrates that the PLZST ceramic has a typical tetragonal AFE phase structure [6,18]. The inset (b) displays the surface SEM image of the ceramic. It can be seen that the ceramic is very dense and the average grain size is about 2–3μm. These indicate that the PLZST ceramic can withstand a high breakdown electric field, which is crucial for obtaining superior energy storage properties, according to Eqs. (1) and (2) given above.

Fig. 1.

The XRD pattern of the PLZST AFE ceramic. The insets (a) and (b) show respectively the fine XRD pattern in the 2θ rang of 43–45° and the surface SEM image of the ceramic.


The PE hysteresis loops, and W, Wre, η of the PLZST AFE ceramics under different electric fields at room temperature are respectively shown in Fig. 2(a) and Fig. 2(b). The inset in Fig. 2(a) gives the Pmax, Pr, and ΔP (PmaxPr) as a function of the applied electric field. As seen, all PE loops are slim, which well accords to our expectation, and thus leading to high η. Besides, it is obvious that, with increasing applied electric field, the Pmax, Pr, Wre, and W continuously rise, while the η slightly reduces. The improvement of the polarization with increasing electric field arises from the fact that the polarization is directly proportional to the electric-field strength, as described by the following equation [19]:

where E is the electric-field strength, D is the electric displacement, ɛr is the relative dielectric constant, and ɛo is the vacuum dielectric constant. Based on this equation and Eqs. (1) and (2), it is known that the energy density is directly proportional to the square of the electric-field strength, which leads to the observed increase of energy density with electric-field strength. At the electric field of 170kV/cm, the ceramic shows simultaneously a large Wre of 3.47J/cm3, and a high η of 78%, which can satisfy practical applications in some circumstances. The dielectric material used in most commercially available film capacitors is the biaxially oriented polypropylene (BOPP) film and its maximum recoverable energy density is 2J/cm3 at 600kV/mm [19–21].

Fig. 2.

(a) PE hysteresis loops and (b) Wre, W, η of the PLZST AFE ceramic under the different electric field at room temperature. The inset shows Pmax, Pr, and ΔP as a function of the applied electric field.


Fig. 3 presents the comparison of room-temperature Wre and η of recently reported (Pb,La)(Zr, Sn,Ti)O3 based AFE ceramics [11,22–31]. As seen, in previously reported work, it is hard to acquire simultaneously a large Wre and a high η in a single material. In contrast, Pb0.97La0.02(Zr0.50Sn0.43Ti0.07)O3 AFE ceramics with high Sn content reported in this work exhibit simultaneously a reasonably large Wre and a fairly high η, which makes it overall superior to most lead-based AFE ceramics in terms of energy-storage properties.

Fig. 3.

Comparison of energy densities and efficiencies of recently reported (Pb,La)(Zr,Sn,Ti)O3 based AFE ceramics.


Due to inevitable temperature variation during the capacitor operation, the energy storage capacity of dielectric materials must be high in a wide temperature range. We thus investigate how the temperature affects energy-storage properties of the PLZST AFE ceramic. Fig. 4(a) shows PE hysteresis loops of the ceramic at temperatures in the range of 20–120°C. As seen, with increasing temperature, the hysteresis loop gradually slims down, which indicates that a large Wre and high η may be obtained at high temperatures. Besides, when the measuring temperature rises, both Pmax and Pr decrease slowly. This is attributed to the weakened AFE phase stability, as revealed by the temperature-dependent dielectric constant measurement (the inset in Fig. 4(a)). Fig. 4(b) shows the current vs. electric-field (IE) curve, from which the EF, corresponding to the peak value of the positive current, and the EA, corresponding to the peak value of the negative current, can be determined. It is obvious that both EA and EF gradually decrease with increasing temperature, which can also be attributed to the weakened AFE phase stability.

Fig. 4.

Temperature-dependence of the (a) PE hysteresis loops and (b) IE curves of the PLZST AFE ceramic. The inset gives the permittivity vs. temperature curve of the ceramic.


Fig. 5(a), (b), and (c) shows respectively the polarization, phase-transition electric field, energy density, and energy efficiency as a function of the temperature. As seen, with increasing temperature from 20 to 120°C, the maximum polarization decreases from 34.22μC/cm2 to 27.03μC/cm2, which results in the decrease of the W. However, the energy efficiency increases from 82.4% to 86.3% because of the reduction of the electrical hysteresis (ΔE=EFEA). As a result, the Wre keeps beyond 1.87J/cm3 in the wide temperature range of 20–120°C. This character is important for developing dielectric capacitors capable of working in different conditions.

Fig. 5.

(a) Pmax, Pr, ΔP, (b) EF, EA, ΔE, and (c) W, Wre, η of the PLZST AFE ceramic during the temperature range of 20–120°C.


In summary, in this work, we designed and fabricated Pb0.97La0.02(Zr0.50Sn0.43Ti0.07)O3 AFE ceramics with high Sn content. The ceramic exhibited typical tetragonal phase structure and dense microstructure. By studying energy storage capacity of this material at different applied electric fields, it was found that a large room-temperature recoverable energy storage density of 3.47J/cm3 together with a high energy efficiency of 78% could be simultaneously realized because the Sn element can slim PE loops of the ceramic. Besides, the energy storage capacity of the ceramic remains superior in the wide temperature range of 20–120°C. All these indicate that Pb0.97La0.02(Zr0.50Sn0.43Ti0.07)O3 AFE ceramics have great potential in making pulsed power capacitors working in different conditions.

Conflicts of interest

The authors declare no conflicts of interest..


This work was supported by the National Natural Science Foundation of China (Grant Nos. 61274010, 51572073, 51602093, 11774082, 51872079), the Natural Science Foundation of Hubei Province (Grant Nos. 2016AAA031, 2018CFB700), Wuhan Application Foundation Frontier Project (No. 2018010401011287), and State Key Laboratory of Advanced Technology for Materials Synthesis and Processing (Wuhan University of Technology; Grant No. 2018-KF-16).

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These authors contributed equally to the work.

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