Achieving high energy storage performance below 200 kV/cm in BaTiO3-based medium-entropy ceramics

A small applied electric field is particularly crucial in the practical application of dielectric ceramic capacitors, since it means a longer lifetime of the capacitors in practical energy storage applications. Based on the traditional ferroelectric BaTiO₃, the (1-x)(Ba_0.6Na_0.2Bi_0.2)TiO₃-xNaNbO₃ medium-entropy material is designed in this paper, which correlates configuration entropy with energy storage performance. The findings demonstrate that the BNBT-0.15NN ceramic synchronously achieves high energy storage density (2.95 J/cm³) and the energy storage efficiency (95.2%) at 180 kV/cm when the configuration entropy rises to 1.43R. The idea of medium-entropy energy storage under low electric field is proposed for the first time, opening up a new avenue for research into the preparation of high energy storage dielectric ceramics via exploring medium-entropy composition.     

Large electrocaloric effect in lead-free Ba1-xCaxTi1-yZryO3 ceramics under strong electric field at room-temperature

In this study, lead-free Ba_1-xCa_xZr_yTi_1-yO₃ (BCTZ(x, y)) ceramics were prepared by means of the classic solid-state reaction method. The morphotropic phase transition (MPB) from the orthorhombic to the tetragonal phase (O-T) was identified in this composition. Besides, the identification of those two structures at room temperature (RT) was made possible thanks to an X-ray diffraction (XRD) study. In order to determine the phase transitions dielectric measurements were conducted. Based on Maxwell equation, the electrocaloric (EC) effect in the studied ceramics was performed via the indirect method. The compositions gave maximum EC temperature changes (ΔT) at above their T_C on application of a 3?kV/mm electric field. These temperature changes are ΔT?=?0.565?K at T_EC=?392?K, ΔT?=?0.548?K at T_EC=?365?K and ΔT?=?0.235?K at T_EC=?307?K for BCZT(10%,5%), BCZT(13%,10%) and BCZT(20%,15%), respectively. At RT, these compositions provided a very interesting EC coefficient (ξ?=?ΔT/ΔE) compared to the pure BaTiO₃ (BT). These values, lying between 0.105 Kmm/kV and 0.188Kmm/kV for ΔE?=?3?kV/mm, are also greater than those related to some lead-based ferroelectric.     

Novel non-equimolar SrLa(Al0.25Zn0.125Mg0.125Ga0.25Ti0.25)O4 high-entropy ceramics with excellent mechanical and microwave dielectric properties

Novel non-equimolar high-entropy SrLa(Al_0.25Zn_0.125Mg_0.125Ti_0.25Ga_0.25)O₄ (SLAZMTG) ceramics with a layered perovskite structure have been prepared via the standard solid-state reaction method. The high-entropy composition belongs to the tetrahedral structure with a space group of I4/mmm, which is confirmed by the XRD and TEM analyses. Excellent microwave dielectric properties with a suitable dielectric constant (ε_r = 22.5), high quality factor (Qf = 83,003 GHz), and near-zero τ_f value of −1.7 ppm/°C are obtained in SLAZMTG ceramics sintered at 1400 °C. Meanwhile, a significant enhancement in compressive strength was achieved due to the improvement of configuration entropy, 912 MPa for SLAZMTG compared to 578 MPa in the pure SrLaAlO₄ composition. Additionally, the high-entropy engineering in the present work suggests great potential in achieving low thermal conductivities. SLAZMTG ceramics exhibit low thermal conductivities ranging from 2.86 W/m•K at 323 K to 1.99 W/m•K at 673 K, much lower than those of SrLaAlO₄ and other perovskite ceramics.     

A novel high-entropy perovskite ceramics Sr0.9La0.1(Zr0.25Sn0.25Ti0.25Hf0.25)O3 with low thermal conductivity and high Seebeck coefficient

In this work, a novel high-entropy n-type thermoelectric material Sr_0.9La_0.1(Zr_0.25Sn_0.25Ti_0.25Hf_0.25)O₃ with pure perovskite phase was prepared using a conventional solid state processing route. The results of TEM and XPS show that various types of crystal defects and lattice distortions, such as oxygen vacancies, edge dislocations, in-phase rotations of octahedron and antiparallel cation displacements coexist in this high-entropy ceramic. At 873 K, the high-entropy ceramics showed both a low thermal conductivity (1.89 W/m/K) and a high Seebeck coefficient (393 μV/K). This work highlights a way to obtain high-performance perovskite-type oxide thermoelectric materials through high-entropy composition design.     

Non-ergodic – ergodic transition and corresponding electrocaloric effect in lead-free bismuth sodium titanate-based relaxor ferroelectrics

The ferroelectric refrigeration technology based on electrocaloric effect (ECE) is a promising environmental way to replace the gas compression refrigeration. Lead-free bismuth sodium titanate (NBT)-based relaxor ferroelectric ceramics have advantages of a large ECE within a wide temperature range around the depolarization temperature (T_d), but the T_d of pure NBT is too high to meet the application requirements. Here, we systematically studied the electrocaloric effect in (0.95-x)(Na_0.5Bi_0.5)TiO₃-0.05SrTiO₃-x(K_0.5Na_0.5)NbO₃ ((0.95-x)NBT-0.05ST-xKNN) ceramics and its relation with the relaxor behavior. The addition of KNN enhances the relaxor character, and shifts the T_d from 120 °C to a low temperature even below 0 °C. The directly measured ECE shows a peak of high ?T_max = 0.88 K (@ 60 °C) for x = 0.05 under an electric field of 40 kV/cm and a wide temperature span of 79 °C (≥ 80% of ?T_max). The x = 0.07 sample exhibits the optimal room-temperature ECE performance with a high ?T_30 °C = 0.71 K because the non-ergodic – ergodic phase transition occurs near room temperature. The electric field–temperature phase diagram reveals the origin of the enhanced ECE as the electric-field-induced transition between polar nanoregions (PNRs) and long-range ferroelectric domain.     

Composition dependent structure,dielectric and energy storage properties of Pb(Tm1/2Nb1/2)O3-Pb(Mg1/3Nb2/3)O3 antiferroelectric ceramics

In order to stabilize the perovskite structure and improve the storage energy density (U) of Pb(Tm_1/2Nb_1/2)O₃ (PTmN) based materials, Pb(Mg_1/3Nb_2/3)O₃ (PMN) was introduced into PTmN to form binary (1-x)PTmN-xPMN solid solution ceramics. The XRD patterns show that all the compositions belong to orthorhombic phase with space group Pbnm. The Curie temperature (T_C) gradually decreases while the dielectric constant (ε') increases for (1-x)PTmN-xPMN with increasing PMN content. The ε' of each composition above T_C obeys the Curie-Weiss law. The appearance double hysteresis loop confirms the antiferroelectric nature of (1-x)PTmN-xPMN (x = 0.02–0.18) ceramics. With the increase of PMN concentration, the maximum polarization slowly increases from 8.58 μC/cm² to 29.5 μC/cm² while the threshold electric field (E_A-F) gradually declines from 290 kV/cm to 120 kV/cm. The maximum of U (3.12 J/cm³) is obtained in 0.92PTmN-0.08PMN ceramic with moderate E_A-F = 220 kV/cm, which makes (1-x)PTmN-xPMN ceramics safe in practical application.     

Multilayer 0.9Pb(Mg1/3Nb2/3)O3–0.1PbTiO3 elements for electrocaloric cooling

Electrocaloric (EC) cooling elements in the form of multilayers (MLs) were prepared. The elements consist of five layers of the relaxor-ferroelectric 0.9Pb(Mg_1/3Nb_2/3)O₃–0.1PbTiO₃, about 60 μm thick, with internal platinum electrodes and exhibiting a dense, uniform microstructure with a grain size of 1.7 μm. The largest temperature change ΔT_EC of 2.26 K was achieved at an electric field (E) of 100 kV cm⁻¹ and at 105 °C, measured by a high-resolution calorimeter. These results agree well with the indirect measurements. The EC coefficient, ΔT_EC/ΔE, obtained for the MLs, is similar to the value obtained for bulk ceramics of the same composition. The ΔT_EC values above 2 K over a broad temperature range from 75 to 105 °C make the ML elements suitable candidates for EC cooling devices at significantly lower voltages than bulk ceramic plates with comparable dimensions and mass.     

Ultrahigh electric breakdown strength,excellent dielectric energy storage density,and improved electrocaloric effect in Pb-free (1-x)Ba(Zr0.15Ti0.85)O3-xNaNbO3 ceramics

In this study, NaNbO₃ (NN) was introduced into Ba(Zr_0.15Ti_0.85)O₃ (BZT) to form a solid solution with relaxor ferroelectric characteristics. The dielectric breakdown strength (BDS) of the specimen with 6 mol.% NN reached 680 kV/cm, the corresponding recoverable energy storage density (W_rec) was 5.15 J/cm³, and the energy storage efficiency (η) was 77%. The dissolution of Na ⁺ ions at the A position and Nb⁵⁺ ions at the B position of the perovskite structure reduced the concentration of oxygen vacancies in the lattice and compensated for defects. The doped ceramics exhibited lower dielectric loss and better thermal stability: the W_rec value was 2 ± 1% J/cm³ at 30–120 °C. In particular, in the 0.02NN ceramics, a ΔT of 1.81 K was achieved at 130 kV/cm, and the operating temperature zone expanded with the increase in doping concentration. The introduction of NN resulted in BZT ceramics that possess excellent energy storage performance and electrocaloric effect properties.     

Achieving outstanding temperature stability in KNN-based lead-free ceramics for energy storage behavior

Lead-free ceramics with prominent energy storage properties are identified as the most potential materials accessed in the dielectric capacitors. Nevertheless, high recoverable energy storage density (W_rec), large energy storage efficiency (η) and preferable temperature stability can hardly be met simultaneously. The Bi(Zn_2/3Ta_1/3)O₃ and NaNbO₃ components are doped in KNN ceramics to substantiate the reliability of this tactic. A high recoverable energy density (W_rec) of ～ 4.55 J/cm³ and a large energy storage efficiency (η) of ～ 87.8% are acquired under the dielectric breakdown strength (DBS) of ～ 375 kV/cm, along with a splendid thermal stability (W_rec variation: ～ 2.3%, η variation: ～ 4.9%) within the temperature range of 20 ℃? 120 ℃. This article demonstrates that the KNN-based ceramics integrate high energy storage properties and outstanding temperature stability at the same time, which broadens the application fields of pulse power systems.     

The electrocaloric effect of Ba1-xLaxTi0.9Sn0.1O3 ceramics with excellent temperature stability near room temperature

The Ba_1-xLa_xTi_0.9Sn_0.1O₃ ceramics (x = 0, 0.006, 0.007, 0.008) were prepared by the traditional solid-state reaction method. The influence of La³⁺ on the phase, dielectric properties, ferroelectric properties, and electrocaloric effect (ECE) was analyzed in detail. The results of refinement show that all ceramics are multiphase coexistence at room temperature, including the cubic phase, the tetragonal phase, and the orthogonal phase. With the increase of La³⁺, the polar phases decrease but the non-polar phase increases, which is the main reason for the decline in adiabatic temperature change (ΔT). The analysis of dielectric properties and ferroelectric properties demonstrate that the diffuse phase transition is strengthened by introducing La³⁺. It also means that polar nanoregions (PNRs) might be formed. Therefore, the temperature stability of the Ba_1-xLa_xTi_0.9Sn_0.1O₃ ceramics in a wide temperature range near room temperature is improved. Simultaneously, the PNRs provide additional entropy to improve ECE. A higher ΔT = 0.88 K is obtained under 60 kV/cm for x = 0.007, which also possesses excellent temperature stability in the temperature range of 298 K–378 K. The doping of La³⁺ also improves the electric field threshold of the electrocaloric strength (ΔT_max/ΔE) and stabilizes the ΔT_max/ΔE under a higher electric field, which is conducive to improving ECE under a higher electric field and providing another possible solution for promoting the practical application of ECE.     

A medium-entropy perovskite oxide La0.7Sr0.3Co0.25Fe0.25Ni0.25Mn0.25O3-δ as intermediate temperature solid oxide fuel cells cathode material

In this study, we report a novel medium-entropy perovskite oxide of La_0.7Sr_0.3Co_0.25Fe_0.25Ni_0.25Mn_0.25O_3-δ (LSCFNM73) with high constitutive entropy (S_config) as the cathode material of intermediate temperature solid oxide fuel cells (IT-SOFCs). The intrinsic properties of phase structure, electrical conductivity, thermal expansion and oxygen adsorption capacity of La_1-xSr_xCo_0.25Fe_0.25Ni_0.25Mn_0.25O_3-δ (LSCFNM, x = 0, 0.1, 0.2, 0.3) oxides are evaluated in detail. The LSCFNM73 oxide exhibits the maximum electrical conductivity of 464 S cm⁻¹ at 800 °C and a relatively lower thermal expansion coefficient (TEC) of 15.34 × 10⁻⁶ K⁻¹, which is selected as the propriate cathode composition. The B-site of LSCFNM73 contains four elements which can increase the configuration entropy. Additionally, NiO-Yttria stabilized zirconia (YSZ) supported fuel cell is fabricated by tape casting, hot pressing-lamination, co-sintering and screen printing technologies. The fuel cell demonstrates a maximum power density of 1088 mW cm² at 800 °C, and excellent stability at 750 °C under 0.75V in 120 h and 10 times thermal cycling between 750 °C and 400 °C. Therefore, the medium-entropy LSCFNM73 oxide can be applied in IT-SOFCs as a competitive cathode material.     

Microstructure and dielectric properties of perovskite-structured high-entropy ceramics of Pb(Zr0.25Ti0.25Sn0.25Hf0.25)O3

A dielectric high-entropy ceramic with a composition of Pb(Zr_0.25Ti_0.25Sn_0.25Hf_0.25)O₃ was designed through B-site doping, and then prepared by solid phase reaction method combined with conventional sintering in air for 3 h at 1200 ^°C, 1250 ^°C and 1300 ^°C, respectively. All the high-entropy ceramics of Pb(Zr_0.25Ti_0.25Sn_0.25Hf_0.25)O₃ possess a perovskite structure with uniform elemental distribution and their average grain size falls within the range of 3.19–5.5 μm. For the sample sintered at 1250 ^°C, the dielectric loss is less than 0.07 in the testing frequency of 1 kHz∼1 MHz in 30–350 ^°C, and the dielectric constant reaches a peak of 14356 at about 270 ^°C at 1 kHz. At room temperature, the remnant polarization P_r reaches 28.8 μC/cm². The results demonstrate that the high-entropy ceramic of Pb(Zr_0.25Ti_0.25Sn_0.25Hf_0.25)O₃ has great potentials in the dielectric and ferroelectric field.     

Combustion synthesis of high-performance high-entropy dielectric ceramics for energy storage applications

High-entropy dielectric ceramics have demonstrated a promising prospect for applications in energy storage recently. However, most high-entropy dielectrics synthesized by conventional solid-state reaction (SSR) method demonstrated unsatisfactory performance for energy storage. Therefore, it is meaningful to develop a feasible way to fabricate high-performance high-entropy dielectric ceramics. Herein, high-entropy (Sr_0.6Bi_0.2Na_0.2)(Ti_1-xZr_x/2Al_x/4Nb_x/4)O₃ ceramics are prepared by a solution combustion synthesis (SCS) method. The SCS fabricated ceramics (x = 0.25) demonstrate a high recoverable energy density of ∼4.46 J/cm³ at a high critical electric field of 520 kV/cm, a high energy efficiency ∼88.52%, a large power density of ∼176.65 MW/cm³ (at 400 kV/cm), an ultrafast discharge time of ∼48 ns, and a high Vikers hardness of ∼7.09 GPa. The key energy storage parameters are much better than those of the samples prepared by the SSR method owing to the absence of unexpected impurity phases, and the refined grain size at the submicrometer scale in our SCS fabricated high-entropy ceramics. The study provides a facile way to fabricate high-performance high-entropy dielectric ceramics for energy storage, indicating that the SCS routine is notably advantageous for preparing high-entropy dielectric energy ceramics.     

Enhanced dielectric energy storage performance of A-site Ca2+-doped Na0.5Bi0.5TiO3–BaTiO3–BiFeO3 Pb-free ceramics

(1-x) (0.98Na_0.5Bi_0.5TiO₃–0.01BaTiO₃–0.01BiFeO₃)–xCaTiO₃ (NBB-xCT) ceramics were produced using traditional solid-state synthesis methods. The surface morphology, domain structure, and electrical properties of the ceramic samples were systematically studied. In addition, the temperature and frequency stabilities of the NBB-15CT sample at 200 kV/cm were tested. Generally, NBB-xCT ceramics exhibit a typical single perovskite phase structure. The results indicate that the NBB-15CT ceramics showed a high energy density of 3.14 J/cm³ at 250 kV/cm. The piezoresponse force microscopy (PFM) results showed that the addition of CT broke the macrodomains of the 0.98Na_0.5Bi_0.5TiO₃-0.01BaTiO₃-0.01BiFeO₃ ceramic and helped to form nanodomains, leading to an improved energy storage performance. The above performance indicates that the specimens possess very good temperature-and frequency-dependent energy storage performances at 30–150 °C and 1–100 Hz. Moreover, the electric energy storage and release in the NBB-15CT ceramic indicated that the power density could reach 55.30 MV/cm³ at 180 kV/cm. Therefore, the NBB-15CT ceramic is a promising material for electrical capacitors.     

Synthesis and characterizations of KNN ferroelectric ceramics near 50/50 MPB

Lead free ferroelectric ceramics near the morphotropic phase boundary (MPB) of K_xNa_1?x(NbO₃)/KNN system (where x=0.48, 0.50, 0.52) were synthesized in the single perovskite phase by the partial co-precipitation synthesis route. The compositional dependences of phase, structure and electrical properties were studied in detail. X-ray diffraction (XRD) study revealed the coexistence of orthorhombic and monoclinic structures in K_0.50N_0.50NbO₃. SEM characterization of the sintered KNN ceramics revealed dense and homogeneous packing of grains. Room temperature (RT) dielectric constant (ε_r) ～648, dielectric loss (tan δ) ～0.05 at 100 kHz, a relatively high density (ρ) ～4.49 g/cm³, remnant polarization (P_r) ～11.76 μC/cm², coercive field (E_c) ～9.81 kV/cm, Curie temperature (T_c) ～372 °C and piezoelectric coefficient (d₃₃) ～71 pC/N observed in K_0.50N_0.50NbO₃ suggested that it can be an important lead free ferroelectric material.     

Structure and electrical properties of Ce-modified Ca1-xCexBi2Nb1.75(Cu0.25W0.75)0.25O9 high Curie point piezoelectric ceramics

Ca_1-xCe_xBi₂Nb_1.975(Cu_0.25W_0.75)_0.025O₉ (CBNCW-xCe: x = 0.00, 0.02, 0.04, 0.06, and 0.09) lead-free piezoelectric ceramics with improved piezoelectric properties were prepared by the traditional solid-state reaction method. The effects of CeO₂ doping on the microstructure and electrical properties were investigated in detail. XRD patterns and Rietveld refinement show that the crystal structures of the samples transform from the orthorhombic phase into the pseudotetragonal phase and that the lattice distortion is weakened. Raman and XPS spectra indicate that Ce ions exist with +3 and + 4 valences in the air sintered ceramics, in which Ce⁴⁺ replaces Nb⁵⁺, causing the weakened NbO₆ octahedral vibration of torsional and tensile and an increase in oxygen vacancies in the doped ceramics. When x = 0.04, it shows excellent comprehensive properties with a high d₃₃ value of 18.1 pC/N, a T_c value of 900 °C, and a ρ_dc value of 2.8 × 10⁵ Ω cm at 500 °C. Our results suggest that the CBNCW-0.04Ce ceramic is a promising candidate in high-temperature piezoelectric applications.     

Densification behavior and electrical properties of CuO-doped Pb(In1/2Nb1/2)O3–Pb(Mg1/3Nb2/3)O3–PbTiO3 ternary ceramics

CuO modified Pb(In_1/2Nb_1/2)O₃–Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ (PIN–PMN–PT) ternary relaxor based ferroelectrics with the composition near the morphotropic phase boundary were synthesized by two-step columbite precursor method. The introduction of CuO significantly improved the sinterability of PIN–PMN–PT ceramics, resulting in the full densification of samples at lower sintering temperatures. It also profoundly modified the crystal structure and fracture mode of the ceramics. Properly increasing CuO content led to the disappearance of rhombohedral-tetragonal phase transition, remarkably improved the Curie temperature (T_c), and made the ceramics more relaxorlike. The ternary ceramics doped with 0.25 wt% CuO possessed optimum piezoelectric properties (d₃₃=584 pC/N, d₃₃^*=948 pC/N, and k_p=0.68), high ferroelectric properties (E_c=9.9 kV/cm, and P_r=33.1 μC/cm²), low dielectric loss (tan δ=0.9%), and wider temperature usage range (T_c=225 °C). The obtained properties are much higher than those of previously reported PIN–PMN–PT based ceramics, indicating that CuO doped PIN–PMN–PT is a promising candidate for electromechanical applications with high performance and wide temperature/electric field usage ranges.     

Effect of CuO Addition on the Microstructure and Electric Properties of Low‐Temperature Sintered 0.25PMN–0.40PT–0.35PZ Ceramics

Low‐temperature sintering of 0.25PMN–0.40PT–0.35PZ ceramics was investigated using CuO as a sintering aid. Effect of CuO on the sinterability, microstructure, and electric properties of 0.25PMN–0.40PT–0.35PZ system was systematically studied. The CuO addition significantly reduced the sintering temperature of 0.25PMN–0.40PT–0.35PZ from 1260°C to 950°C. SEM results indicated that a dense microstructure without any second phase was obtained when the amount of CuO was 0.25 wt%, which gave rise to high values of d₃₃ = 532 pC/N and k_p = 58.4%. A large field‐induced longitudinal strain ~2.28% (at 30 kV/cm) can also be obtained for 0.25 wt% CuO‐added specimens, which shows a great promise for multilayer actuator applications.     

Enhanced energy storage performance and temperature stability achieved by a synergic effect in Nd3+/Ga3+ co-doped (Na0.5Bi0.5)TiO3 -based ceramics

(1-x)(0.75(Na_0.5Bi_0.5)TiO₃-0.25SrTiO₃)-xNdGaO₃ ceramics (NBST-xNG, x = 0–0.06) were fabricated through a solid-state reaction method. High-valent Nd³⁺ ions enter the perovskite A-site to occupy Bi vacancies resulting from the volatilization of Bi, inhibiting the formation of oxygen vacancies and contributing to an enhanced breakdown electric field (E_b). Low-valent Ga³⁺ ions enter the B-site to substitute for Ti⁴⁺ ions, resulting in the formation of random electric fields (REFs) at the B-site due to co-occupying hetero-valence ions of Ga³⁺/Ti⁴⁺, which significantly reduces ferroelectric hysteresis. Therefore, a synergic effect of A- and B-sites co-doping was realized in NBST-xNG ceramics. Benefitting from this synergic effect, an enhanced recoverable energy storage density (W_rec) of 2.88 J/cm³ and an efficiency (η) of 83% are simultaneously obtained in NBST-0.04NG ceramics under a moderate electric field (E) of 200 kV/cm. Compared with most NBT-based ceramics, the values of (η vs W_rec/E²) for NBST-0.04NG ceramics show an obvious advantage, indicating excellent potential for application as an energy storage material. Moreover, W_rec and η of NBST-0.04NG ceramics exhibit excellent temperature stability from 30 °C to 200 °C due to the enhanced correlation strength of polar nanoregions (PNRs) and local structural stability. This work provides a potential strategy to improve the energy storage performance of NBT-based ceramics via the synergic effect of A- and B-site co-doping.     

Improved energy storage properties of Sr(Zr0.8Nb0.16)O3-doped Bi0.47Na0.47Ba0.06TiO3 ceramics with excellent temperature/frequency stability

Lead-free perovskite dielectric materials for capacitors have received wide concern in recent years, but their energy storage density and efficiency still cannot meet the growing application demand for practical applications. In this work, we prepared a lead-free relaxor ferroelectric ceramic of (1-x)Bi_0.47Na_0.47Ba_0.06TiO₃-xSr(Zr_0.8Nb_0.16)O₃, which was synthesized via a normal solid-state route. The microstructure, dielectric properties and energy storage behavior of the ceramics were explored. The ceramics can be well sintered and situated in the region where rhombohedral and tetragonal phases coexist. The addition of Sr(Zr_0.8Nb_0.16)O₃ (SZN) significantly extends the dielectric-temperature plateau between T_s and T_m and reduces the remnant polarization P_r, but the large saturation polarization P_s is still maintained. Besides, the doping of SZN enhances the relaxation of the material and increases the dielectric breakdown strength (DBS) from 50 kV/cm (x = 0) to 100 kV/cm (x = 0.04 and 0.06). Therefore, the ceramic with x = 0.06 exhibits a high discharging efficiency (η) of 71.1% and energy density (W) of 1.56 J/cm³ at 100 kV/cm and shows the superior thermal stability with the changes in recoverable energy density (W_rec) and η of less than 10% and 30% at the temperature range of 25–180 °C and the excellent frequency stability with the variations of W_rec and η of less than 1.8% and 1% at the frequency range of 10 Hz–100 Hz.