Ultrahigh Energy Storage Density and Efficiency of Lead-Free Dielectrics with Sandwich Structure.

Lead-free dielectric capacitors have attracted significant research interest for high-power applications due to their environmental benefits and ability to meet the demanding performance requirements of electronic devices. However, the development of lead-free ceramic dielectrics with outstanding energy storage performance remains a challenge. In this study, environmentally friendly ceramic dielectrics with sandwich structures are designed and fabricated to improve energy storage performance via the synergistic effect of different dielectrics. The chemical compositions of the outer and middle layers of the sandwich structure are 0.35BiFeO3 -0.65SrTiO3 and Bi0.39 Na0.36 Sr0.25 TiO3 , respectively. The experimental and theoretical simulation results demonstrate that the breakdown strength is over 700 kV cm-1 for prepare sandwich structure ceramics. As a result, an ultrahigh recoverable energy storage density of 9.05 J cm-3 and a near-ideal energy storage efficiency of 97% are simultaneously achieved under 710 kV cm-1 . Furthermore, the energy storage efficiency maintains high values (≥ 96%) within 1-100 Hz and the power density as high as 188 MW cm-3 under 400 kV cm-1 . These results indicate that the designed lead-free ceramics with a sandwich structure possess superior comprehensive energy storage performance, making them promising lead-free candidates in the energy storage field.

Local Isomeric Polar Nanoclusters Enabled Superior Capacitive Energy Storage Under Moderate Fields in NaNbO3-Based Lead-Free Ceramics.

The high-field energy-storage performance of dielectric capacitors has been significantly improved in recent years, yet the high voltage risks of device failure and large cost of insulation technology increase the demand for high-performance dielectric capacitors at finite electric fields. Herein, a unique superparaelectric state filled with polar nanoclusters with various local symmetries for lead-free relaxor ferroelectric capacitors is subtly designed through a simple chemical modification method, successfully realizing a collaborative improvement of polarization hysteresis, maximum polarization, and polarization saturation at moderate electric fields of 20-30 kV mm-1. Therefore, a giant recoverable energy density of ≈5.0 J cm-3 and a high efficiency of ≈82.1% are simultaneously achieved at 30 kV mm-1 in (0.9-x)NaNbO3-0.1BaTiO3-xBiFeO3 lead-free ceramics, showing a breakthrough progress in moderate-field comprehensive energy-storage performances. Moreover, superior charge-discharge performances of high-power density ≈182 MW cm-3, high discharge energy density ≈4.3 J cm-3 and ultra-short discharge time <70 ns as well as excellent temperature stability demonstrate great application potentials for dielectric energy-storage capacitors in pulsed power devices. This work provides an effective and paradigmatic strategy for developing novel lead-free dielectrics with high energy-storage performance under finite electric fields.

High Energy Storage Performance in BiFeO3-Based Lead-Free High-Entropy Ferroelectrics.

Dielectric capacitors are widely used in advanced electrical and electronic systems due to the rapid charge/discharge rates and high power density. High comprehensive energy storage properties are the ultimate ambition in the field of application achievements. Here, the high-entropy strategy is proposed to design and fabricate single-phase homogeneous (Bi0.5Ba0.1Sr0.1Ca0.2Na0.1)(Fe0.5Ti0.3Zr0.1Nb0.1)O3 ceramic, the hierarchical heterostructure including rhombohedral-tetragonal multiphase nanoclusters and locally disordered oxygen octahedral tilt can lead to the increased dielectric relaxation, diffused phase transition, diverse local polarization configurations, grain refinement, ultrasmall polar nanoregions, large random field, delayed polarization saturation and improved breakdown field. Accordingly, a giant Wrec ≈13.3 J cm-3 and a high η ≈78% at 66.4 kV mm-1 can be simultaneously achieved in the lead-free high-entropy BiFeO3-based ceramic, showing an obvious advantage in overall energy-storage properties over BiFeO3-based lead-free ceramics. Moreover, an ultrafast discharge rate (t0.9 = 18 ns) can be achieved at room temperature, concomitant with favorable temperature stability in the range of 20-160 °C, due to the enhanced diffuse phase transition and fast polarization response. This work provides a feasible pathway to design and generate dielectric materials exhibiting high comprehensive energy-storage performance.

Realizing Outstanding Energy Storage Performance in KBT-Based Lead-Free Ceramics via Suppressing Space Charge Accumulation.

The great potential of K1/2Bi1/2TiO3 (KBT) for dielectric energy storage ceramics is impeded by its low dielectric breakdown strength, thereby limiting its utilization of high polarization. This study develops a novel composition, 0.83KBT-0.095Na1/2Bi1/2ZrO3-0.075 Bi0.85Nd0.15FeO3 (KNBNTF) ceramics, demonstrating outstanding energy storage performance under high electric fields up to 425 kV cm-1: a remarkable recoverable energy density of 7.03 J cm-3, and a high efficiency of 86.0%. The analysis reveals that the superior dielectric breakdown resistance arises from effective mitigation of space charge accumulation at the interface, influenced by differential dielectric and conductance behaviors between grains and grain boundaries. Electric impedance spectra confirm the significant suppression of space charge accumulation in KNBNTF, attributable to the co-introduction of Na1/2Bi1/2ZrO3 and Bi0.85Nd0.15FeO3. Phase-field simulations reveal the emergence of a trans-granular breakdown mode in KNBNTF resulting from the mitigated interfacial polarization, impeding breakdown propagation and increasing dielectric breakdown resistance. Furthermore, KNBNTF exhibits a complex local polarization and enhances the relaxor features, facilitating high field-induced polarization and establishing favorable conditions for exceptional energy storage performance. Therefore, the proposed strategy is a promising design pathway for tailoring dielectric ceramics in energy storage applications.

Gradient-Structured Ceramics with High Energy Storage Performance and Excellent Stability.

Owing to the high power density, eco-friendly, and outstanding stability, the lead-free ceramics have attracted great interest in the fields of pulsed power systems. Nevertheless, the low energy storage density of such ceramics is undoubtedly a severe problem in practical applications. To overcome this limitation, the lead-free ceramics with gradient structures are designed and fabricated using the tape-casting method herein. By optimizing the composition and distribution of the gradient-structured ceramics, the energy storage density, and efficiency can be improved simultaneously. Under a moderate electric field of 320 kV cm-1 , the value of recoverable energy storage density (Wrec ) is higher than 4 J cm-3 , and the energy storage efficiency (η) is of ≥88% for 20-5-20 and 20-10-20. Furthermore, the gradient-structured ceramics of 20-10-0-10-20 and 20-15-0-15-20 possess high applied electric field, large maximum polarization, and small remnant polarization, which give rise to ultrahigh Wrec and η on the order of ≈6.5 J cm-3 and 89-90%, respectively. In addition, the energy storage density and efficiency also exhibit excellent stability over a broad range of frequencies, temperatures, and cycling numbers. This work provides an effective strategy for improving the energy storage capability of eco-friendly ceramics.

Composition and Structure Optimized BiFeO3 -SrTiO3 Lead-Free Ceramics with Ultrahigh Energy Storage Performance.

Dielectric ceramic capacitors have attracted increasing attention as advanced pulsed power devices and modern electronic systems owing to their fast charge/discharge speed and high power density. However, it is challenging to meet the urgent needs of lead-free ceramics with superior energy storage performance in practical applications. Herein, a strategy for the composition and structural modification is proposed to overcome the current challenge. The lead-free ceramics composed of BiFeO3 -SrTiO3 are fabricated. A low hysteresis and high polarization can be achieved via composition optimization. The experimental results and finite element simulations indicate that the two-step sintering method significantly influences the decrease in the grain size and improvement in the breakdown strength (EBDS ). A high EBDS of ≈750 kV cm-1 accompanied by a large maximum polarization (≈40 µC cm-2 ) and negligible remanent polarization (<2 µC cm-2 ) contribute to the ultrahigh energy density and efficiency values of the order of 8.4 J cm-3 and ≈90%, respectively. Both energy density and efficiency exhibit excellent stability over the frequency range of 1-100 Hz and temperatures up to 120 °C, along with the superior power density of 280 MW cm-3 , making the studied BiFeO3 -SrTiO3 ceramics potentially useful for high-power energy storage applications.

Boosting Energy Storage Performance of Lead-Free Ceramics via Layered Structure Optimization Strategy.

Owing to the current global scenario of environmental pollution and the energy crisis, the development of new dielectrics using lead-free ceramics for application in advanced electronic and energy storage systems is essential because of the high power density and excellent stability of such ceramics. Unfortunately, most of them have low breakdown strength and/or low maximum polarization, resulting in low energy density and efficiency. To overcome this limitation here, lead-free ceramics comprising a layered structure are designed and fabricated. By optimizing the distribution of the layered structure, a large maximum polarization and high applied electric field (>500 kV cm-1 ) can be achieved; these result in an ultrahigh recoverable energy storage density (≈7 J cm-3 ) and near ideal energy storage efficiency (≈95%). Furthermore, the energy storage performance without obvious deterioration over a broad range of operating frequencies (1-100 Hz), working temperatures (30-160 °C), and fatigue cycles (1-104 ). In addition, the prepared ceramics exhibit extremely high discharge energy density (4.52 J cm-3 ) and power density (405.50 MW cm-3 ). Here, the results demonstrate that the strategy of layered structure design and optimization is promising for enhancing the energy storage performance of lead-free ceramics.

Real-Time Capturing of Microscale Events Controlling the Sintering of Lead-Free Piezoelectric Potassium-Sodium Niobate.

Sintering is a very important process in materials science and technological applications. Despite breakthroughs in achieving optimized piezoelectric properties, fundamentals of K0.5 Na0.5 NbO3 (KNN) sintering are not yet fully understood, facing densification versus grain growth competition. At present, microscale events during KNN sintering under reducing atmospheres are real-time monitored using a High Temperature-Environmental Scanning Electron Microscope. A two contacting KNN particles model satisfying the Kingery and Berg's bulk diffusion model is reported. Dynamic events like individual grain growth and grain elimination process are explored through a postanalysis of recorded image series. The diffusion coefficient for oxygen vacancies of 10-8 cm2 s-1 and average boundary mobility of 10-9 cm4 J-1 s-1 are reported for the KNN ceramics. Moreover, the local pore shrinkage is consistent with the Kingery and François's concept of pore stability except that pore curvatures are not all concave, convex or flat due to anisotropic grain-boundary energies. The global grain growth kinetics are described using parabolic and/or cubic laws. The effect of atmospheres and microstructure evolution on the intrinsic and extrinsic contributions to the dielectric response using Rayleigh's law is also explored. These results bring a new breath for KNN sintering studies in order to adapt the sintering process.

Lead-Free AE Sensor Based on BZT-BCT Ceramics.

In this study, an acoustic emission (AE) sensor was fabricated using lead-free Ba(Zr0.2Ti0.8)O3-0.5(Ba0.7Ca0.3)TiO3 (BZT-BCT) ceramics. The acoustic and electromechanical properties of the AE sensor were determined by the shapes of the piezoelectric ceramics. To optimize the AE sensor performance, the shapes of the ceramics were designed according to various diameter/thickness ratios (D/T) = 0.5, 1.0, 1.5, 2.0, 2.5, 3.0. The BZT-BCT ceramic with D/T = 1.0 exhibited excellent values of a piezoelectric charge coefficient (d33), piezoelectric voltage coefficient (g33), and electromechanical coupling factor (kp), which were 370 (pC/N), 11.3 (10-3 Vm/N), and 0.58, respectively. Optimum values of resonant frequency (fr) = 172.724 (kHz), anti-resonant frequency (fa) = 196.067 (kHz), and effective electromechanical coupling factor (keff) = 0.473 were obtained for the manufactured BZT-BCT ceramic with D/T = 1.0. The maximum sensitivity and frequency of the AE sensor made of the BZT-BCT ceramic with a D/T ratio of 1.0 were 65 dB and 30 kHz, respectively.

Synthesis and high-frequency magnetoelectric characterization of the 0-3 particulate lead-free multiferroic composite KNN/CFO.

The research for lead-free magnetoelectric (ME) multiferroic composite materials has increased considerably because they are environmentally friendly. For composites with 0-3 connectivity, synthesis with lead-free phase has proven challenging to obtain high values of ME coupling. This work reports the successful synthesis of the KNN/CFO composite (K0.5N0.5NbO3/CoFe2O4) by conventional synthesis process. XRD and SEI showed two well-defined, also presenting good electric polarization values. The ME coefficient was very high, reaching values close to 2850 mV cm-1·Oe at the electromechanical resonance frequency. The dipolar interaction between the electric charges and magnetic moments of the KNN and CFO phases was responsible for the high value and the behavior of dependence on the applied magnetic field.

Simultaneous Improvement of Energy Storage Characteristics and Temperature Stability in K0.5Na0.5NbO3-Based Ceramics via LiF Modification.

The splendid energy storage performances with eminent stability of dielectric ceramics utilized in pulsed power devices have been paid more attention by researchers. This scheme can be basically realized through introducing Li+, Bi(Mg2/3Ta1/3)O3, NaNbO3, and LiF into KNN-based ceramics. Under the breakdown strength (BDS) of 460 kV/cm, an outstanding energy storage density (W) of 6.05 J/cm3 with a high energy efficiency (η) of 85.9% is implemented. Within the broad temperature range from 20 to 140 °C, the numerical fluctuations of energy storage characteristics can be maintained at a relatively stable level (ΔWrec ≈ 3.5%, Δη ≈ 2.8%). As for the charging-discharging performances, this component possesses a fast discharging speed (t0.90 ≈ 51 ns) and remarkable temperature stability (the variations are smaller than 3.5%). Additionally, the internal mechanisms of outstanding energy storage properties can be confirmed via crystal structures and domain structures, the content of oxygen vacancies, dielectric and impedance spectra, and phase simulation. Hence, the combination of outstanding energy storage with remarkable thermal stability can be fulfilled in one ceramic system according to this discovery, providing a research thought of developing the materials for dielectric capacitors.

Achieving Ultrahigh Electrocaloric Response in (Bi0.5Na0.5)TiO3-Based Ceramics through B-Site Defect Engineering.

Lead-free electrocaloric (EC) ferroelectrics are considered ideal for the next generation of environmentally friendly solid-state refrigeration materials. However, their inferior performance compared to lead-based materials significantly restricts their potential application. According to phase-field simulations, it is predicted that the pinning effect of a moderate number of defects can effectively enhance the reversible polarization response associated with the entropy change. Herein, sodium-bismuth titanate (BNT) ceramics with high spontaneous polarization are selected to construct B-site defects by introducing Li+ and Nb5+. Under an electric field of 6 kV mm-1, ultrahigh EC temperature changes of ΔTpos = 1.77 and ΔTneg = 1.49 K are achieved at 65 °C by direct measurement (ΔTneg > 1 K over 55-120 °C). Furthermore, ΔTneg remains above 0.70 K in the temperature range from 25 to 130 °C, exhibiting immense potential for practical applications. This study offers a promising direction for optimizing the EC response in defect systems.

Ultrahigh Energy-Storage Density of BaTiO3-Based Ceramics via the Interfacial Polarization Strategy.

Lead-free dielectric capacitors are excellent candidates for pulsed power devices. However, their low breakdown strength (Eb) strongly limits their energy-storage performance. In this study, Sr0.7Bi0.2TiO3 (SBT) and Bi(Mg0.5Hf0.5)O3 (BMH) were introduced into BaTiO3 (BT) ceramics to suppress interfacial polarization and modulate the microstructure. The results show that the introduction of SBT and BMH increases the band gap width, reduces the domain size, and, most importantly, successfully attenuates the interfacial polarization. Significantly enhanced Eb values were obtained in (1 - x)(0.65BaTiO3-0.35Sr0.7Bi0.2TiO3)-xBi(Mg0.5Hf0.5)O3 (BSBT-xBMH) ceramics. Meanwhile, the interfacial polarization was reduced to near zero in the sample with x = 0.10, achieving an ultrahigh Eb (64 kV/mm) and a very large recoverable energy-storage density (Wrec ≈ 9.13 J/cm3). In addition, the sample has excellent thermal stability (in line with EIA-X7R standards) and frequency stability. These properties indicate that the BSBT-0.10BMH ceramic holds promising potential for the application of pulsed power devices.

Substantially Enhanced Electrocaloric Effect in Ba(Zr0.2Ti0.8)O3 Lead-Free Ferroelectric Ceramics via Lattice Stress Engineering.

As an alternative to conventional vapor-compression refrigeration, cooling devices based on electrocaloric (EC) materials are environmentally friendly and highly efficient, which are promising in realizing solid-state cooling. Lead-free ferroelectric ceramics with competitive EC performance are urgently desirable for EC cooling devices. In the past few decades, constructing phase coexistence and high polarizability have been two crucial factors in optimizing the EC performance. Different from the external stress generated through heavy equipment and inner interface stress caused by complex interface structures, the internal lattice stress induced by ion substitution engineering is a relatively simple and efficient means to tune the phase structure and polarizability. In this work, we introduce low-radius Li+ into BaZr0.2Ti0.8O3 (BZT) to form a particular A-site substituted cell structure, leading to a change of the internal lattice stress. With the increase of lattice stress, the fraction of the rhombohedral phase in the rhombohedral-cubic (R-C) coexisting system and ferroelectricity are all pronouncedly enhanced for the Li2CO3-doped sample, resulting in the significant enhancement of saturated polarization (Ps) as well as EC performance [e.g., adiabatic temperature change (ΔT) and isothermal entropy change (ΔS)]. Under the same conditions (i.e., 333 K and 70 kV cm-1), the ΔT of 5.7 mol % Li2CO3-doped BZT is 1.37 K, which is larger than that of the pure BZT ceramics (0.61 K). Consequently, in cooperation with the great improvement of electric field breakdown strength (Eb) from 70 to 150 kV cm-1, 5.7 mol % Li2CO3-doped BZT achieved a large ΔT of 2.26 K at a temperature of 333 K, which is a competitive performance in the field of electrocaloric effect (ECE). This work provides a simple but effective approach to designing high-performance electrocaloric materials for next-generation refrigeration.

Significantly Enhanced Energy Storage Performance of Lead-Free BiFeO3-Based Ceramics via Synergic Optimization Strategy.

Owing to the merits of giant power density and ultrafast charge-discharge time, dielectric capacitors including ceramics and films have inspired increasing interest lately. Nevertheless, the energy storage density of dielectric ceramics should be further optimized to cater to the boosting demand for the compact and portable electronic devices. Herein, an ultrahigh recoverable energy storage density Wrec of 13.44 J/cm3 and a high efficiency η of 90.14% are simultaneously realized in BiFeO3-BaTiO3-NaTaO3 relaxor ferroelectric ceramics with high polarization Pmax, reduced remanent polarization Pr, and optimized electric breakdown strength Eb. High Pmax originates from the genes of BiFeO3-based ceramics, and reduced Pr is induced by enhanced relaxor behavior. Particularly, a large Eb is achieved by the synergic contributions from complicated internal and external factors, such as decreased grain size and improved resistivity and electrical homogeneity. Furthermore, the ceramics also exhibit satisfactory frequency, cycling and thermal reliability, and decent charge-discharge property. This work not only indicates that the BiFeO3-based relaxor ferroelectric materials are promising choices for the next-generation electrostatic capacitors but also paves a potential approach to exploit novel high-performance dielectric ceramics.

Ultrahigh Polarization Response along Large Energy Storage Properties in BiFeO3-BaTiO3-Based Relaxor Ferroelectric Ceramics under Low Electric Field.

BiFeO3-BaTiO3 (BF-BT) dielectric ceramics are receiving more and more concern for advanced energy storage devices owing to their excellent ferroelectric properties and environmental sustainability. However, the energy density and efficiency are limited in spite of the large remanent polarization. Herein, we proposed a multiscale optimization strategy via a local compositional disorder with a Birich content and nanodomain engineering by introducing the Sr0.7Bi0.2Ca0.1TiO3 (SBCT) into BF-BT ceramics. Interestingly, an extraordinary energy storage property (ESP) with a high reversible energy storage density (Wrec) of ∼3.79 J/cm3 and an ultrahigh polarization discrepancy (ΔP) of ∼58.5 µC/cm2 were obtained in the SBCT-modified BF-BT ceramics under 160 kV/cm. The boosted ESP should be attributed to the fact that the replacement of A/B-sites cations could transform the long-range ferroelectric order of the BF-BT system into polar nanoregions (PNRs) along with the refined grain size, decreased leakage current, and broadened energy band gap. Moreover, good frequency (1-103 Hz) and temperature (25-125 °C) stabilities, high fatigue resistance (× 105), large power density (∼31.1 MW/cm3), and fast discharge time (∼97 ns) were also observed for the optimized ceramics. These results illustrate a potentially effective method for creating high ESP lead-free ceramics at a low electric field.

Enhanced Piezoelectric Properties in a Single-Phase Region of Sm-Modified Lead-Free (Ba,Ca)(Zr,Ti)O3 Ceramics.

In ferroelectric materials, phase boundaries such as the morphotropic phase boundary (MPB) and polymorphic phase boundary (PPB) have been widely utilized to enhance the piezoelectric properties. However, for a single-ferroelectric-phase system, there are few effective paradigms to achieve the enhancement of piezoelectric properties. Herein, we report an unexpected finding that largely enhanced piezoelectric properties occur in a single-tetragonal-ferroelectric-phase region in the Sm-modified (Ba0.85Ca0.15)(Zr0.1Ti0.9)O3 (BCZT-xSm) system. An electrostrain maximum (0.13%) appears in the single-phase region of the BZCT-0.5Sm composition with the maximum polarization (Pm = 18.37 µC/cm2) and piezoelectric coefficient (d33 = 396 pC/N) and the minimum coercive field (EC = 3.30 kV/cm) at room temperature. Such an enhanced piezoelectric effect is due to the synergistic effect of large lattice distortion and domain miniaturization on the basis of the transmission electron microscope (TEM) observation and X-ray diffraction (XRD) Rietveld refinement. Our work may provide new insights into the design of high-performance ferroelectrics in the single-phase region.

Ultrahigh Energy-Storage Performances in Lead-free Na0.5Bi0.5TiO3-Based Relaxor Antiferroelectric Ceramics through a Synergistic Design Strategy.

Dielectric ceramics with outstanding energy-storage performances are nowadays in great demand for pulsed power electronic systems. Here, we propose a synergistic design strategy to significantly enhance the energy-storage properties of (1 - x)(0.94Na0.5Bi0.5TiO3-0.06BaTiO3)-xCaTi0.75Ta0.2O3 solid solution ceramics through introducing polar nanoregions, shifting rhombohedral to tetragonal phase transition below room temperature (stable antiferroelectric characteristic), as well as increasing the band gap in the system. Ultrahigh energy-storage properties with a record value of recoverable energy-storage density Wrec ∼ 9.55 J/cm3 and a high efficiency η ∼ 88% are achieved in Na0.5Bi0.5TiO3-based bulk ceramics with x = 0.24. Moreover, high Wrec (>3.4 J/cm3) and η (>90%) with a variation of less than 6% can be observed in a wide frequency and temperature frequency range of 5-200 Hz and 25-140 °C. Our research result not only indicates the great possibility of Na0.5Bi0.5TiO3-based lead-free compositions to replace lead-based energy-storage ceramics but also gives an effective strategy to design ultrahigh energy-storage performances for eco-friendly ceramics.

Enhanced Pyroelectric Performance of Lead-Free Zn-Doped Na1/2Bi1/2TiO3-BaTiO3 Ceramics.

Lead-free Na1/2Bi1/2TiO3-BaTiO3 (NBT-BT) has gained revived interest due to its exceptionally good high power properties in comparison to commercial lead-based piezoelectrics. Recently, Zn-modified NBT-BT-based materials as solid solution and composites have been reported to exhibit enhanced depolarization temperatures and a high mechanical quality factor. In this work, the pyroelectric properties of Zn-doped NBT-6mole%BT and NBT-9mole%BT ceramics are investigated. The doped compositions of NBT-6BT and NBT-9BT feature a relatively stable pyroelectric property in a wide temperature range of ~37 K (300-330 K) and 80 K (300-380 K), respectively. A threefold increase in detector figure of merit is noted for 0.01 mole Zn-doped NBT-6mole% BT at room temperature in comparison to undoped NBT-6mole%BT and this increase is higher than those of major lead-free materials. A broad range of the temperature-independent behavior for the figures of merit was noted (303-380 K) for Zn-doped NBT-6mole% BT, which is 30 K higher than the undoped material. The large pyroelectric figures of merit and good temperature stability renders Zn-doped NBT-BT an ideal candidate for pyroelectric detector and energy harvesting applications.

Improved Non-Piezoelectric Electric Properties Based on La Modulated Ferroelectric-Ergodic Relaxor Transition in (Bi0.5Na0.5)TiO3-Ba(Ti, Zr)O3 Ceramics.

The characteristic transition from ferroelectric (FE) to ergodic relaxor (ER) state in (Bi0.5Na0.5)TiO3 (BNT) based lead-free ceramics provides an efficient approach to bring a highly ordered phase back to a disordered one. It would be rational to utilize this transition to improve relevant non-piezoelectric properties based on domain decomposition. In this work, different La contents were introduced to 0.93(Bi0.5Na0.5)TiO3-0.07Ba(Ti0.945Zr0.055)O3 ceramics (BNT-BZT-xLa) to induce evolution of ergodic degree. The results reveal that with increasing La content, both the FE-ER transition temperature TF-R and depolarization temperature Td shift towards room temperature, implying a deepened ergodic degree. By modulation of ergodic degree, thermally stimulated depolarization current experiment shows a higher current density peak, and corresponding pyroelectric coefficient increases from 2.46 to 2.81 µC/(cm2∙°C) at Td. For refrigeration, the indirect measurement demonstrates the ΔT maximum increases from 1.1 K to 1.4 K, indicating an enhanced electrocaloric effect. Moreover, the optimized energy storage effect is observed after La doping. With appearance of "slimmer" P-E loops, both calculated recoverable energy storage density Wrec and storage efficiency η increase to 0.23 J/cm3 and 22.8%, respectively. These results denote La doping conduces to the improvement of non-piezoelectric properties of BNT-based ceramics in a certain range. Therefore, La doping should be an adopted modification strategy for lead-free ceramics used in areas like refrigerator and pulse capacitors.