High energy storage density and efficiency in nanostructured (Bi0.2Na0.2K0.2La0.2Sr0.2)TiO3 high-entropy ceramics

High-entropy ceramics (HECs) (Bi_0.2Na_0.2K_0.2La_0.2Sr_0.2)TiO₃ (BNKLST) with single-phase perovskite structure have been successfully prepared by a modified citrate acid method. In comparison to (Bi_0.5Na_0.5)TiO₃ (BNT) ceramics prepared by the same synthesis route, the BNKLST HECs exhibit dense nanostructures with grain sizes as small as 45 nm, which are suggested to be responsible for the significantly improved electric breakdown fields and reduced leakage currents in the ceramics, and they have much enhanced elastic modulus owing to the entropy-stabilized perovskite structure. The electrical and dielectric characterizations reveal that BNKLST has high electrical resistances and dielectric constants at elevated temperatures, and, in particular, a recoverable energy storage density of 0.959 J/cm³ can be achieved under an applied electric field of 180 kV/cm. Moreover, the energy storage efficiency in BNKLST can be maintained to be larger than 90% at 40–200°C. These excellent properties suggest that entropy-stabilized BNT-based ceramics are promising dielectrics for electrical energy storage applications.     

Enhanced energy-storage properties in Zr4+-modified (Bi0.4Ba0.2K0.2Na0.2)TiO3 high-entropy ceramics

Recently, high-entropy perovskite oxides (HEPOs) have received increasing interest for energy storage applications owing to their unique structure, huge composition space, and promising properties. However, designing HEPOs with improved energy storage performance remains a challenge. In this study, various HEPOs were designed by partially replacing Zr⁴⁺ for Ti⁴⁺ in (Bi_0.4Ba_0.2K_0.2Na_0.2)TiO₃ medium-entropy ferroelectric ceramics. The resulting ceramics exhibited a pseudo-cubic structure. With increasing Zr⁴⁺ content, the ceramics gradually transformed into relaxor ferroelectrics. The energy storage performance of the ceramics depended on the Zr⁴⁺ content. The sample with 20 mol% Zr⁴⁺ showed the best energy storage performance with a maximum reversible energy density of 2.47 J/cm³ and an energy storage efficiency of 82.3% at a low applied electric field (224 kV/cm). This study obtained a promising material for the new generation dielectric energy storage capacitors and provided a novel method for enhancing energy storage performance.     

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.     

High energy-storage performance of lead-free Ba0.4Sr0.6TiO3–Sr0.7Bi0.2TiO3 relaxor-ferroelectric ceramics with ultrafine grain size

Relaxor-ferroelectric (RFE) ceramics possess slender ferroelectric hysteresis loop and low remnant polarization (P_r). They have great potential to provide excellent energy-storage performance as dielectric energy-storage materials. Herein, a lead-free 0.8Ba_0.4Sr_0.6TiO₃–0.2Sr_0.7Bi_0.2TiO₃ (0.8BST–0.2SBT) RFE ceramic with high energy-storage performance has been realized successfully. The addition of Bi³⁺ and increase in Sr²⁺content at the A site of the BST can effectively inhibit the growth of grains for high breakdown strength (E_b). As a result, an ultrafine average grain size of 0.7 μm was obtained in 0.8BST–0.2SBT RFE ceramic, affording a high E_b of 300 kV/cm. Further investigation revealed that the mutual conversion of short-range polar nanoregions and long-range-ordered ferroelectric domains upon application and withdrawal of a 300 kV/cm applied electric field resulted in a high maximum polarization (P_max) of 31 μC/cm² and a low P_r of 2.5 μC/cm². Hence, the 0.8BST–0.2SBT RFE ceramic simultaneously exhibited a high recoverable energy-storage density of 3.3 J/cm³ and a high energy-storage efficiency of 85% at 300 kV/cm. Additionally, a good energy-storage performance was reported over a temperature range of 50°C-120 °C and frequency from 10 to 1000 Hz, making the 0.8BST-0.2SBT RFE ceramic a potential lead-free dielectric energy-storage material.     

Enhancement in energy storage performance of La-modified bismuth-ferrite-based relaxor ferroelectric ceramics by defect compensation and process optimization

In this investigation, La₂O₃ was doped into 0.85(0.65BF-0.35BT)-0.15Sr_0.7Bi_0.2TiO₃ (BF-BT-SBT) to form a solid solution with relaxation ferroelectric properties. The dielectric breakdown strength (BDS) of 1% mole of La doping was 220 kV/cm, the maximum recoverable energy storage (W_rec) was 2.35 J/cm³, and the energy storage efficiency (η) was 71%. The relationship between ceramic properties and microstructure was investigated in detail. Doping with La has the following main features: (1) The dissolution of La³⁺ ions in the A position of the original perovskite structure reduced the concentration of oxygen vacancies in the lattice and played a role of compensating the defects. (2) The dielectric loss of ceramics was reduced, the impedance was greatly increased, and the specimen exhibited a high-temperature stability: a maximum W_rec of 4.04 ± 1.7% J/cm³ in 30–130 °C. (3) The core–shell–like with single phase structure in La-doped ceramics had been successfully observed, which may become a strategy for preparing high-performance ceramics. Higher BDS and denser structures were obtained in 0.01 La ceramics by further optimizing the preparation of the above compositions by the viscous polymer process (VPP). The BDS of 0.01La ceramics prepared by VPP reached 480 kV/cm, the effective energy storage density reached 6.15 J/cm³, and the η was about 81%. This made La-doped 15SBT (chemical composition of BF-BT-SBT + La₂O₃) ceramics become a potential candidate material for energy storage devices.     

Relaxor Ferroelectric BaTiO3–Bi(Mg2/3Nb1/3)O3 Ceramics for Energy Storage Application

Perovskite solid solution ceramics of (1 ? x)BaTiO₃–xBi(Mg_2/3Nb_1/3)O₃ (BT–BMN) (x = 0.05–0.2) were synthesized by solid‐state reaction technique. The results show that the BMN addition could lower the sintering temperature of BT‐based ceramics. X‐ray diffraction results reveal a pure perovskite structure for all studied samples. Dielectric measurements exhibit a relaxor‐like characteristic for the BT–BMN ceramics, where broadened phase transition peaks change to a temperature‐stable permittivity plateau (from ?50°C to 300°C) with increasing the BMN content (x = 0.2), and slim polarization–electric field hysteresis loops were observed in samples with x ≥ 0.1. The dielectric breakdown strength and electrical resistivity of BT–BMN ceramics show their maxima of 287.7 kV/cm and 1.53 × 10¹³ Ω cm at x = 0.15, and an energy density of about 1.13 J/cm³ is achieved in the sample of x = 0.1.     

Structure,dielectric properties of novel Ba(Zr,Ti)O3 based ceramics for energy storage application

(1-x) Ba(Zr_0.2Ti_0.8)O₃-x Na_0.5Bi_0.5TiO₃ (x = 0, 10, 20 30, 40, 50 mol%) (BZTN) ceramics are prepared by the traditional solid phase method. All BZTN ceramics exhibit a pseudo-cubic BZT based perovskite structure. Both the average grain size and the relaxor ferroelectricity of BZTN ceramics gradually increase with increasing NBT content. The W_rec of 3.22 J/cm³ and η of 91.2% is obtained for the BZTN40 ceramic at 241 kV/cm. BZTN40 ceramic also exhibits good temperature stability from room temperature to 150 °C and frequency stability from 1 Hz to 100 Hz. A P_D of 0.621 J/cm³ and a t_0.9 of 82 ns is obtained for the BZTN40 ceramic at 120 kV/cm. BZTN ceramics show application potential in energy storage and pulse power capacitors.     

Effect of ZnO doping on the microstructure and microwave dielectric properties of 0.2CaTiO3-0.8(Li0.5Sm0.5)TiO3 ceramics

0.2CaTiO₃-0.8(Li_0.5Sm_0.5)TiO₃-xZnO(x = 0, 0.3, 0.6, 0.9, 1.2 wt%, 0.2CT-0.8LST-xZnO) with orthogonal perovskite structure were fabricated by the solid state method. The effects of ZnO additives on the microwave dielectric properties of 0.2CT-0.8LST ceramics were systematically investigated. With increasing the dopant (x) concentration, the dielectric constant (ε_r) and the temperature co-efficient of resonance frequency (τ_f) decreased, however, the Q × f values increased. The relationship between vibration mode and microwave dielectric properties was studied using Raman spectroscopy. The Q × f value of ceramics was related to the half-height width of Raman scattering. Narrower Raman scattering peaks corresponded to longer microwave energy propagation decay times and higher Q × f value. Based on X-ray photoelectron spectroscopy (XPS), the addition of Zn²⁺ ions limited the reduction of Ti⁴⁺ cations. The excellent dielectric properties were obtained when x = 1.2 wt% with ε_r = 100.25, Q × f = 6525 GHz, and τ_f = ?12.12 ppm/°C.     

Novel (Sm0.2Lu0.2Yb0.2Y0.2Dy0.2)3TaO7 high-entropy ceramic for thermal barrier coatings

A novel (Sm_0.2Lu_0.2Dy_0.2Yb_0.2Y_0.2)₃TaO₇ (SLT-5RE_0.2) oxide with a single-fluorite structure was synthesized via an optimized sol-gel and sintering method, and its crystal structure, mechanical and thermophysical properties were investigated. The results indicate that the calcined nanoscale powder is of high crystallinity, and bulk sample is of a uniform elemental distribution. Compared to YSZ (6–8 wt.% Y₂O₃ partially stabilized by ZrO₂), SLT-5RE_0.2 exhibits lower Young's modulus, less mean acoustic velocity, and higher Vickers microhardness. Owing to the strengthened anharmonic vibration and phonon scattering, SLT-5RE_0.2 exhibits low thermal conductivity (1.107 W K^?1·m^?1, 900 °C). The high thermal expansion coefficient (11.3 × 10^?6 K^?1, 1200 °C) of SLT-5RE_0.2 ceramic can be ascribed to the reduced lattice energy and ionic spacing as well as the cocktail effect of high-entropy ceramics. The excellent mechanical and thermophysical properties, and excellent phase steadiness during the whole testing temperature cope, indicate that SLT-5RE_0.2 high-entropy ceramic can be a candidate material for thermal barrier coatings.     

The effect of rare-earth oxides on the energy storage performances in BaTiO3 based ceramics

In this work, 0.7BaTiO₃-0.3Sr_0.2Bi_0.7TiO₃ (0.7BT-0.3SBT) ceramics with 0.15 mol% various rare-earth oxides doped are designed and synthesized by the conventional solid-state route. All prepared samples exhibited a single perovskite phase and dense microstructure with fine grain size (0.2–0.5 μm) after sintering at 1180 °C. Especially, the Gd-doped 0.7BT-0.3SBT ceramics exhibited excellent energy storage performances; the corresponding recoverable energy density and efficiency were 3.2 J/cm³ and 91.5% under an electric field of 330 kV/cm, respectively. Meanwhile, doping with Gd caused the BT-based ceramics to possess excellent temperature (30–150 °C) and outstanding frequency stabilities (10–1000 Hz). Moreover, the pulsed charge-discharge experiments revealed that a high power density of 59 MW/cm³ and a fast discharge speed of 110 ns with outstanding temperature stability could be synchronously obtained in the Gd-doped composition. All these features are attractive for pulsed power applications.     

Synthesis,structure, and dielectric properties of a new binary antiferroelectric solid solution: (1−x)Pb(Mg1/2W1/2)O3–xPbHfO3

Dielectric ceramics are one of the most important electrical insulators because of their excellent electrical stability and nonconducting properties. In this work, new complex perovskite solid solutions, (1−x)Pb(Mg_1/2W_1/2)O₃–xPbHfO₃ [(1−x) PMW–xPHf] (0.00 ≤ x ≤ 0.04), were successfully synthesized in the form of ceramics by the solid-state reaction method and sintering process. The X-ray diffraction results indicate that a single perovskite phase with antiferroelectric (AFE) orthorhombic Pmcn symmetry is formed for x < 0.04 which corresponds to the PMW-type solid solution (SS-PMW). For the composition x = 0.04, however, a small amount (about 1%) of ferroelectric orthorhombic C2mm phase that arises from the PHf-type solid solution (SS-PHf) was found to coexist with the Pmcn phase (99%). The dielectric measurements show that the AFE-paraelectric phase transition temperature T_C of the (1−x)PMW–xPHf ceramics increases from 38.2°C (x = 0) to 40.1°C (x = 0.03) with the increasing PHf content, indicating a slightly enhanced AFE ordering degree. The studied materials show a relatively low dielectric constant (~10²), a low dielectric loss (~10⁻²), a high breakdown field strength (~140 kV/cm), and a linear electric field dependence of polarization at room temperature, which make them a new candidate for potential applications as ceramic insulators.     

Enhanced piezoelectric strain of BiFeO3–Ba(Zr0.02Ti0.98)O3 lead-free ceramics near the phase boundary

The xBiFeO₃-(1-x)Ba(Zr_0.02Ti_0.98)O₃ + 1.0 mol% MnO₂ (xBF-BZT) lead-free piezoelectric ceramics were prepared by conventional solid-state reaction method. The structure, dielectric, and piezoelectric properties were studied. X-ray diffraction (XRD) analysis showed that xBF-BZT ceramics exhibited pure perovskite structure with the coexistence of tetragonal and rhombohedral phases (0.66 ≤ x ≤ 0.74). The Curie temperature T_c, the dielectric constant ε_r (1 kHz), dielectric loss tanδ (1 kHz), piezoelectric constant d₃₃, coercive field E_c (80 kV/cm), and remnant polarization P_r (80 kV/cm) of 0.7BF-0.3BZT-Mn ceramics were 491°C, 633, 0.044, 165 pC/N, 35.6 kV/cm, and 22.6 μC/cm², respectively. The unipolar strain of 0.7BF-0.3BZT reached up to 0.20% under the electric field of 60 kV/cm, which is larger than that (0.15%) of BiFeO₃–BaTiO₃ ceramics. These results indicated that the xBF-BZT ceramics were promising candidates for high-temperature piezoelectric materials.     

Improved dielectric energy storage performance of Na0.5Bi0.5TiO3–Sr0.7Nd0.2TiO3 lead-free ceramics by adding an appropriate amount of AgNbO3

Based on the significant advantages of dielectric ceramics in high power energy storage, (1-x) (0.55Bi_0.5Na_0.5TiO₃-0.45Sr_0.7Nd_0.2TiO₃)-xAgNbO₃ (NBSNT-xAN) ceramics were prepared by traditional solid phase method. The introduction of AN in NBSNT ceramics not only increased the degree of relaxation, but also refined the grain size, enhanced the BDS, and finally improved the energy storage performance. It is found that the NBSNT-0.5AN ceramics obtained an effective energy storage density as high as 3.08 J/cm³ and an efficiency of 79.94%. In addition, good thermal stability and temperature stability were exhibited in the range of 30–120 °C and 10–350 Hz, and at the same time, it performed very well in the pulsed test at room temperature and variable temperatures. This provides a design idea for the miniaturization and integration of energy storage ceramic materials.     

Marked reduction in the thermal conductivity of (La0.2Gd0.2Y0.2Yb0.2Er0.2)2Zr2O7 high-entropy ceramics by substituting Zr4+ with Ti4+

The (La_0.2Gd_0.2Y_0.2Yb_0.2Er_0.2)₂(Zr_1-xTi_x)₂O₇ (x = 0–0.5) high-entropy ceramics were successfully prepared by a solid state reaction method and their structures and thermo-physical properties were investigated. It was found that the high-entropy ceramics demonstrate pure pyrochlore phase with the composition of x = 0.1–0.5, while (La_0.2Gd_0.2Y_0.2Yb_0.2Er_0.2)₂Zr₂O₇ shows the defective fluorite structure. The sintered high-entropy ceramics are dense and the grain boundaries are clean. The grain size of high-entropy ceramics increases with the Ti⁴⁺ content. The average thermal expansion coefficients of the (La_0.2Gd_0.2Y_0.2Yb_0.2Er_0.2)₂(Zr_1-xTi_x)₂O₇ high-entropy ceramics range from 10.65 × 10^?6 K^?1 to 10.84 × 10^?6 K^?1. Importantly, the substitution of Zr⁴⁺ with Ti⁴⁺ resulted in a remarkable decrease in thermal conductivity of (La_0.2Gd_0.2Y_0.2Yb_0.2Er_0.2)₂(Zr_1-xTi_x)₂O₇ high-entropy ceramics. It reduced from 1.66 W m^?1 K^?1 to 1.20 W m^?1 K^?1, which should be ascribed to the synergistic effects of mass disorder, size disorder, mixed configuration entropy value and rattlers.     

Enhanced insulation and piezoelectric properties of 0.57(Bi0.8La0.2)FeO3-0.43PbTiO3 solid solutions with Fe addition

0.57(Bi_0.8La_0.2)FeO₃-0.43PbTiO₃-x mol%Fe₂O₃ ceramics (BLF-PT-xFe, x = 0, 0.025, 0.05, 0.125, and 0.25) were prepared by the conventional solid-state reaction method. X-ray diffraction (XRD) reveals that all samples display the perovskite structure with a coexistence of tetragonal (T) phase and rhombohedral (R) phase, while the incorporation of Fe promotes the phase transition from T to R. Scanning electron microscopy (SEM) images show that all samples are well crystallized and their grain size increases noticeably with the increase of Fe content. X-ray photoelectron spectroscopy (XPS) results indicate that Fe doping significantly inhibits the formation of oxygen vacancies, thereby improving insulation of BLF-PT-xFe ceramics. Interestingly, the Curie temperature of BLF-PT-xFe is around 330°C, little changing with the variation of Fe content. However, the depolarization temperatures of BLF-PT ceramics with Fe are 50°C higher than that of the sample without Fe doping. The hopping of second ionized oxygen vacancies are the major carriers in the temperature range of 200°C–500°C. The optimal component of BLF-PT-xFe ceramics appear at x = 0.05, where the dielectric loss tanδ, AC resistivity (200°C), and piezoelectric coefficient d₃₃ could be 0.015, 7 × 10⁶ Ω cm, and 245 pC/N, respectively. All these results indicate that the Fe addition is an effective method to enhance dielectric and piezoelectric properties.     

Investigations of the divalent metal ions Zn2+, Co2+, Ni2+ doped ultra-wide temperature stable BBNN system

Multi-component BaTiO₃–Bi_0.5Na_0.5TiO₃–Nb₂O₅ (BBNN) system doped with divalent metal ions (Zn²⁺, Co²⁺, Ni²⁺) was prepared by the conventional solid–state method.The X-ray diffraction patterns revealed all samples exhibited perovskite (P4mm) single phase. The dielectric properties and micro-mechanisms were discussed and validated. Novel theories, based on the characteristics of the different kinds of dielectric polarization, are proposed to explain the dielectric anomalies in the dielectric system. The relationships between microstructure and the dielectric properties were investigated systematically for the first time. The samples doped with 15 mol% Zn²⁺/Co²⁺presented good dielectric properties of an ultra-broad temperature stable range (from −50 and >300), high dielectric constant (ε~1925 for Zn²⁺/ ε~1341 for Co²⁺) and low dielectric loss (tan δ<0.02) were obtained. These features made the ceramics system have high practical values for miniaturization and harsh environments applications.     

New Antiferroelectric Solid Solution of Pb(Mg1/2W1/2)O3–Pb(Zn1/2W1/2)O3 as Dielectric Ceramics

A new solid solution of (1?x)Pb(Mg_1/2W_1/2)O₃–xPb(Zn_1/2W_1/2)O₃ has been prepared in the form of ceramics by solid‐state reaction with composition x up to 30%. It is found that with the substitution of Zn²⁺ for Mg²⁺ on the B site of the of complex perovskite structure the antiferroelectric (AFE) Curie temperature T_C of PMW increases from 40°C (x = 0) to 67°C (x = 30%), indicating an enhancement of antiferroelectric order, whereas, at the same time, the phase transition becomes more diffuse due to a higher degree of chemical inhomogeneity. X‐ray diffraction analysis indicates that the crystal structure adopts an orthorhombic space group (Pmcn) with a decrease in lattice parameter a, but an increase in b and c as the Zn²⁺ concentration increases. The low dielectric constant (~ 10²), low dielectric loss (tanδ ≈ 10^?3), linear‐field‐induced polarization, and significantly high breakdown field (~ 125 kV/cm) at room temperature make this family of dielectric materials a promising candidate for ceramic insulators.     

Effect of substrate temperature on structural and electrical properties of BaZr0.2Ti0.8O3 lead-free thin films by pulsed laser deposition

Barium zirconate titanate (BaZr_0.2Ti_0.8O₃, BZT) 250 nm thick thin films were fabricated by pulsed laser deposition and the influence of the substrate temperature on their preferred orientation, microstructure, morphology and dielectric properties was investigated. Dielectric measurements indicated the (1 1 0)-oriented BZT thin films deposited at 750 °C to show good dielectric properties with high dielectric constant (~500 at 100 kHz), low loss tangent (<0.01 at 100 kHz), and superior tunability (>70% at 400 kV/cm), while the largest figure of merit was 78.8. The possible microstructural background responsible for the high dielectric constant and tenability is discussed. In addition, thin films deposited at 750 °C with device quality factor of 8738 and dielectric nonlinearity coefficient of 1.66×10⁻¹⁰ J/C⁴m⁵ were demonstrated.     

Achieving high energy storage properties in perovskite oxide via high-entropy design

In recent years, “high-entropy” materials have attracted great attention in various fields due to their unique design concepts and crystal structures. The definition of high-entropy is also more diverse, gradually expanding from a single phase with an equal molar ratio to a multi-phase with a non-equimolar ratio. This study selected (Na_0.2Bi_0.2Ba_0.2Sr_0.2Ca_0.2)TiO₃ high entropy ceramics with excellent relaxation behavior. The A-site elements are divided into (x = Na, Bi, Ba) and ((1-3x)/2 = Sr, Ca) according to their inherent properties. A novel ABO₃ structural energy storage ceramics (NaBaBi)_x(SrCa)_(1-3x)/2TiO₃ (x = 0.19, 0.195, 0.2, 0.205 and 0.21) was successfully fabricated using the high entropy design concept. The ferroelectric and dielectric properties of non-equimolar ratio high-entropy ceramics were studied in detail. It was found that the dielectric constant of ∼4920 and the recoverable energy storage density of 3.86 J/cm³ (at 335 kV/cm) can be achieved simultaneously at x = 0.205. The results indicate that the design concept of high-entropy materials with a non-equal molar ratio is an effective means to achieve distinguished energy storage performance in lead-free ceramics.     

Synergistic modification of properties in Ba[(Zn0.8Mg0.2)1/3Nb2/3]O3 ceramics through ordered domain engineering

The ordered domain engineering was investigated for Ba[(Zn_0.8Mg_0.2)_1/3Nb_2/3]O₃ microwave dielectric ceramics to synergistically modify the physical properties especially the temperature coefficient of resonant frequency τ_f and quality factor Q value together with the thermal conductivity. The ordered domain structure could be tailored and controlled by the post-densification annealing, and the fine ordered domain structures with high ordering degree and low-energy domain boundary were obtained in the present ceramics annealed around 1400°C for 24 h, where the Qf value was improved from 51 000 to 118 000 GHz, τ_f was suppressed from 30 to 25.5 ppm/°C. Moreover, the thermal conductivity at room temperature was increased from 3.79 to 4.30 W m⁻¹ K⁻¹, and the Young's modulus was improved from 98 to 214 GPa. The present work provided a promising approach for synergistic modification of physical properties in Ba-based complex perovskite microwave dielectric ceramics.