Structure and energy storage properties of (1-x)Ba0.98Li0.02TiO3 based ceramics with xBi(Mg1/2Sn1/2)O3 addition

doi:10.1016/j.jallcom.2021.161855

Journal of Alloys and Compounds

Volume 891, 25 January 2022, 161855

https://doi.org/10.1016/j.jallcom.2021.161855 Get rights and content

Highlights

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The O phase ratio of BLT-BiMeO₃ affects the polarization.
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Polar nano-regions improve relaxation characteristics.
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The proportion of O phase affects energy storage density.

Abstract

Lead-free ferroelectric ceramics of (1-x)Ba_0.98Li_0.02TiO₃-xBi(Mg_1/2Sn_1/2)O₃ (abbreviated as (1-x)BLT-xBMS, x = 0, 0.02, 0.04, 0.05, 0.06, 0.08) were synthesized through conventional solid-state sintering method. The effects of Bi(Mg_1/2Sn_1/2)O₃ addition on the phase transition, microstructure, the dielectric properties and the energy storage properties were investigated. All the BLT-BMS samples exhibited single phase perovskite structure. XRD and Roman spectrum confirmed the coexistence of the orthorhombic phase and tetragonal phase in the samples with x = 0.00–0.05, which turned to the coexistence of orthorhombic and cubic phase in the samples with x > 0.05. All the samples display dense microstructures with clear grain boundaries. The average grain size of the samples increases and the relaxor characteristics become stronger with the addition of BMS. The existence of orthorhombic phase apparently promotes the energy storage performance. The maximum energy density of 0.16 J/cm³ and the largest energy efficiency of 70.42% were achieved with orthorhombic/tetragonal ratio of 53/47 at x = 0.05.

Introduction

Dielectric ceramic capacitors are considered to be the most potential storage materials for power electronic system because of their high power densities, fast charging-discharging rates, good thermal stability and long cycle lifetimes [1], [2], [3], [4], [5]. During the past decades, lead based ceramic materials such as Pb(Zr,Ti)O₃ (PZT) have dominated in dielectric capacitors due to their outstanding electrical properties, but their further development and application are limited by the toxicity of lead oxides [6], [7], [8], [9]. Consequently, much attention has been paid on BaTiO₃ (BT) based lead-free ceramics for the environmental concern [10], [11], [12]. However, slim polarization-electric field hysteresis loop and near-zero remnant polarization (P_r) become a bottleneck for BT ceramics to achieve superior energy-storage properties. Zhou reported that BT based ceramics such as Ba(Zr,Ti)O₃ and (Ba,Sr)TiO₃ can be transformed from typical ferroelectrics to relaxor ferroelectrics by doping [13], [14]. In considering that the destruction of long-range ordered ferroelectric domains and the formation of polar nano-regions during the transformation process due to different atomic radius, BiMeO₃ were introduced in the BT ceramics where Me representing a trivalent cation or equivalent complex cations such as BiYO_3, Bi(Mg_1/2Zr_1/2)O₃, Bi(Li_0.5Ta_0.5)O₃ and Bi(Mg_1/2Sn_1/2)O₃ [5], [15], [16], [17], [18]. The energy-storage density (W_rec) with 2.25 J/cm³ and energy-storage efficiency (η) with 94% were obtained in the 0.88BaTiO₃–0.12Bi(Mg_1/2Sn_1/2)O₃ ceramics [5].

The creation of moderate oxygen vacancies also contributes to the improvement of energy-storage properties. Tang reported the oxygen-vacancies-related dielectric relaxation behaviors of Bi(Mg_0.5Ti_0.5)O₃ modified BT ferroelectric ceramics, and found that short-range hopping of oxygen vacancy contributed to the dielectric relaxation [19]. Ping further demonstrated the improvement effect of moderate oxygen vacancies on dielectric breakdown strength (BDS) by capturing freely moving charges [20]. In our previous work, oxygen vacancies were created by Li⁺ ions doping through charge compensation mechanism [21]. The BDS value of the Li⁺ ions doped BT ceramic was increased from 39.2 kV/cm to 76.5 kV/cm, and the W_rec and η value of the ceramics were 0.293 J/cm³ and 64.7%, respectively. The ceramics also exhibit refinement effect on grain size and improvement effect on dielectric and piezoelectric properties [22].

Besides the oxygen vacancies and the relaxation behavior, phase transition accompanied with lattice distortion was proved to be essential in modifying piezoelectric and ferroelectric properties in BT based ceramics. Pure BT has three kinds of phase transition process, including rhombohedral-orthorhombic (R-O) phase transition, orthorhombic-tetragonal (O-T) phase transition, and tetragonal-cubic (T–C) phase transition. Yang investigated the (Ba,Ca)(Ti,Zr)O₃ with O–T phase-boundary ceramics, and found that the existence of O phase can sharply decrease the value of the coercive field (E_c) due to its lower lattice distortion than that of T phase [23]. Reversible non-180°domain motion was also discovered in lead-free piezoelectric KNN based ceramics, which facilitated the formation of R-T phase boundary (0.04 <x < 0.05). The nano-scaled domains as well as the domain wall motion promoted the polarization switching [24]. Enhanced piezoelectric properties were achieved by Wang in multiphase(R–O–T) coexisted (1-x) BaTiO₃–xCaZrO₃ ceramics attributed from the internal lattice distortion. More importantly, they found that nano-scaled domains decreased the energy density of domain walls [25]. However, little attention has been paid on the variation of the phase ratio during phase transition process, and there is no detailed research on the relationship between the variation of phase ratio and the energy storage properties.

In this paper, Bi(Mg_1/2Sn_1/2)O₃ was introduced in the Ba_0.98Li_0.02TiO₃ ceramic, and the effects of Bi(Mg_1/2Sn_1/2)O₃ addition on the phase transition, microstructure, dielectric properties as well as energy storage property were analyzed systematically. Multi-phase coexistence system was found to be transformed from T–O phase to O–C phase, the correlation between phase composition and energy storage properties were discussed.

Section snippets

Experimental procedures

The (1-x)(Ba_0.98Li_0.02)TiO₃-xBi(Mg_1/2Sn_1/2)O₃ (x = 0.00–0.08) ceramics were fabricated by conventional solid-state sintering method. BaCO₃ (≥99%, Aladdin), Li₂CO₃ (≥99%, Aladdin), TiO₂ (≥98%, Aladdin), MgO (≥99.9, Aladdin), SnO₂ (≥99.5%, Aladdin) and Bi₂O₃ (≥99.9, Aladdin) powders were used as raw materials. All powders were dried at 120 °C for 12 h and weighed according to stoichiometric formula. Then all weighed powders were mixed with deionized water and ball milled for 10 h with zirconia

Results and discussion

The XRD patterns of (1-x)BLT-xBMS (x = 0.00–0.08) samples were shown in Fig. 1(a). All the sintered samples exhibit perovskite structures, indicating that Bi³⁺, Mg²⁺, Sn⁴⁺ ions diffused into the BLT lattice to form a complete single phase solid solution. Fig. 1(b) shows the enlarged diffraction peaks with 2θ range from 44° to 46° for each component. The samples with x value from 0 to 0.05 exhibit two asymmetric diffraction peaks, which become symmetric at x = 0.06 and 0.08. To identify the

Conclusion

(1-x)Ba_0.98Li_0.02TiO₃-xBi(Mg_1/2Sn_1/2)O₃ (x = 0–0.08) ceramics were synthesized via conventional solid-state sintering method. All the BLT-BMS samples exhibited single phase perovskite structure. The coexistence of the orthorhombic phase and tetragonal phase in the samples with x from 0.00 to 0.05 turned to the coexistence of orthorhombic and cubic phase in the samples with x > 0.05. All the samples display dense microstructures with clear grain boundaries, and the relaxor characteristics become

CRediT authorship contribution statement

Xiao-yu Zhong: Preparation, Investigation, Writing – original draft. Gui-wei Yan: Software, Data curation. Zhi-hui Chen: Supervision, Conceptualization, Methodology, Writing – review & editing.

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgments

The authors wish to acknowledge the financial support of National Natural Science Foundation of China (Grant no. 51702024).

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