Ultralow Electrical Hysteresis along with High Energy‐Storage Density in Lead‐Based Antiferroelectric Ceramics

Abstract

materials (FE), relaxor ferroelectric materials, and antiferroelectric materials (AFEs). [2][3][4][5][6][7] Among them, antiferroelectric materials are preferred candidates for obtaining an exceptional energy storage density due to the high saturation polarization (P s ) and zero remnant polarization (P r ). [7] A schematic illustration of the energy storage mechanism of antiferroelectric materials is shown in Figure S1 in the Supporting Information. The W tot and W rec of antiferroelectrics are calculated by the area between the phase switching loop and the polarization axis and can be described by the following equations [7,8] where P max , P r , and E represent the maximum polarization, the remnant polarization, and applied electric field, respectively. The difference between W rec and W tot represents the energy dissipation (W loss ) and the ratio of W rec to W tot is defined as the energy efficiency, which can be described by the following equation [7,8] 100% 100% rec tot rec rec l ossIn comparison with lead-free antiferroelectric ceramics, PbZrO 3 -based antiferroelectric ceramics have always been a more popular topic because of their superior energy storage performance. It is particularly interesting that a minor variation of doping ions at the A or B site of the perovskite (ABO 3 ) structure may display huge differences in materials properties. Hence, scholars have continuously focused on investigating the structure-property relationships of PbZrO 3 -based AFE ceramics, such as tailoring the phase transition characteristics of AFE ceramics via ions doping, or utilizing unique fabrication methods to increase the energy storage density, and so forth. [8][9][10][11][12] Recently, a record-high recoverable energy storage density of 11.18 J cm −3 was obtained in Sr-doped (Pb 0.94 La 0.02 Sr 0.04 )(Zr 0.9 Sn 0.1 ) 0.995 O 3 AFE ceramics that prepared by tape-casting method. [9] However, the large electrical hysteresis resulted from the first-order antiferroelectric-ferroelectric (AFE-FE) phase transition has always been an apparent drawback of AFE ceramics, [13] leading to the high energy dissipation, Antiferroelectric ceramics with extraordinary energy-storage density have gained exponentially soaring attention for their applications in pulsed power capacitors. Nevertheless, high energy dissipation is a deficiency of antiferroelectric materials. The modulation of Ba/La-doped (Pb 0.91 Ba x La 0.06−2x/3 ) (Zr 0.6 Sn 0.4 )O 3 (x = 0.015, 0.03, 0.045, 0.06) antiferroelectric ceramics is aimed at increasing the energy efficiency and obtaining an ideal energy storage density. The traditional solid-state reaction is exploited for ceramics fabrication and all prepared samples exhibit an ultralow electrical hysteresis due to the local structural heterogeneity, as verified by Raman spectroscopy. Of particular importance is the fact that the (Pb 0.91 Ba 0.045 La 0.03 )(Zr 0.6 Sn 0.4 ) O 3 ceramic possesses an excellent recoverable energy storage density (W rec = 8.16 J cm −3 ) and a remarkable energy efficiency (η = 92.1...

Systematical investigation on energy‐storage behavior of PLZST antiferroelectric ceramics by composition optimizing

“…(A) Temperature dependence of dielectric constant for PLZST‐1 ceramics, (B) Weibull distribution of BDS for PLZST‐4 ceramics, (C)‐(G) SEM images and grain size distributions for PLZST‐4 ceramics, (H) Comparison of W rec and η of AO1 and AT4 in this work with other reported ceramics, in which AO1 is (Pb 0.94 La 0.04 )(Zr 0.99 Ti 0.01 )O 3 in this work; AT4 is (Pb 0.94 La 0.04 )(Zr 0.49 Sn 0.5 Ti 0.01 )O 3 in this work; PBLZS is (Pb 0.91 Ba 0.045 La 0.03 )(Zr 0.6 Sn 0.4 )O 3 27 ; PLSZS is (Pb 0.94 La 0.02 Sr 0.04 )(Zr 0.9 Sn 0.1 ) 0.995 O 3 31 ; BNT‐ST is 0.75(Bi 0.58 Na 0.42 TiO 3 )‐0.25(SrTiO 3 ) 44 ; PLZST is (Pb 0.94 La 0.04 )[(Zr 0.6 Sn 0.4 ) 0.92 Ti 0.08 ]O 3 45 ; PSLZST is (Pb 0.955 Sr 0.015 La 0.02 )(Zr 0.75 Sn 0.195 Ti 0.055 )O 3 46 ; PLZST@SiO2 is Pb 0.97 La 0.02 (Zr 0.33 Sn 0.55 Ti 0.12 )O 3 @5 mol% SiO 2 47 ; BT‐BLT is 0.9BaTiO 3 ‐0.1Bi(Li 0.5 Ta 0.5 )O 3 48 ; PLZT‐M is (Pb 0.91 La 0.06 )(Zr 0.96 Ti 0.04 )O 3 ‐1 mol% MnCO 3 49 ; AN‐BM is AgNbO 3 ‐0.6 mol% BiMnO 3 50 ; STL/BNBT is (SrTiO 3 +Li 2 CO 3 )/(0.94Bi 0.54 Na 0.46 TiO 3 ‐0.06BaTiO 3 ) 51 ; BT‐BMZ is 0.85BaTiO 3 ‐0.15Bi(Mg 0.5 Zr 0.5 )O 3 52 ; PBLYST‐PLZST is (Pb 0.858 Ba 0.1 La 0.02 Y 0.008 )(Zr 0.65 Sn 0.3 Ti 0.05 )O 3 ‐(Pb 0.97 La 0.02 )(Zr 0.9 Sn 0.05 Ti 0.05 )O 3 53 ; ANT is Ag(Nb 0.85 Ta 0.15 )O 3 54 [Color figure can be viewed at wileyonlinelibrary.com]…”

Achieving ultrahigh energy-storage capability in PbZrO3-based antiferroelectric capacitors based on optimization of property parameters

“…, where R A and R B are the ionic radii of the A and B site cations, and R O is the ionic radius of oxygen anion. [32][33][34] It is clear that antiferroelectricity gradually increases with decreasing t. Thus, the reducing the A-site ion radius or increasing the B-site ion radius is benecial to stabilizing the antiferroelectricity. For instance, Liu et al found that the AFE-FE phase transition (E F ) and AFE-FE phase transition eld (E A ) of Mn-doped (Pb 0.87 Ba 0.1 La 0.02 ) (Zr 0.65 Sn 0.3 Ti 0.05 )O 3 ceramics increased from 11.9 to 12.8 kV mm À1 and from 7.6 to 9.3 kV mm À1 , respectively, realizing a W rec of 2.64 J cm À3 .…”

A novel relaxor (Bi,Na,Ba)(Ti,Zr)O3 lead‐free ceramic with high energy storage performance

“…14 A remarkable performance was recently achieved in A-site-deficient (Pb 0.91 Ba 0.045 La 0.03 )(Zr 0.6 Sn 0.4 )O 3 ceramic that possesses an excellent recoverable energy storage density (W rec = 8.16 J/cm 3 ) and energy efficiency (η = 92.1%). 15 Combining the A/B-site modification and tape-casting strategies, the ultrahigh W rec of 11.8 J/cm 3 with a favorable η of 82.2% was achieved in (Pb 0.94 La 0.02 Sr 0.04 )(Zr 0.9 Sn 0.1 ) 0.995 O 3 ceramic. 16 The driving force on the environment concerns urges the development of the alternative lead-free AFE materials such as AgNbO 3 -based ceramics, which, however, only showed a relatively low W rec , being on the order of ~2.0 J/ cm 3 at 140-175 kV/cm, or with a W rec of 4.2 J/cm 3 but η is below 75% in (Ag, La)(Nb, Ta)O 3 ceramics.…”

“…A‐site La‐doped Pb(Zr, Ti)O 3 could generate a high W rec up to 6.4 J/cm 3 , while newly designed B‐site‐modified 0.9PbHfO 3 ‐0.1Pb(Mg 1/2 W 1/2 )O 3 ceramics demonstrate the highest W rec = 3.7 J/cm 3 with a favorable η of 72.5% at a low electric field of 155 kV/cm 14 . A remarkable performance was recently achieved in A‐site‐deficient (Pb 0.91 Ba 0.045 La 0.03 )(Zr 0.6 Sn 0.4 )O 3 ceramic that possesses an excellent recoverable energy storage density ( W rec = 8.16 J/cm 3 ) and energy efficiency ( η = 92.1%) 15 . Combining the A/B‐site modification and tape‐casting strategies, the ultrahigh W rec of 11.8 J/cm 3 with a favorable η of 82.2% was achieved in (Pb 0.94 La 0.02 Sr 0.04 )(Zr 0.9 Sn 0.1 ) 0.995 O 3 ceramic 16 .…”