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.     

Enhanced energy storage properties of BiAlO3 modified Bi0.5Na0.5TiO3–Bi0.5K0.5TiO3 lead-free antiferroelectric ceramics

Lead-free (1−x)(0.75Bi_0.5Na_0.5TiO₃–0.25Bi_0.5K_0.5TiO₃)–xBiAlO₃ (BNT–BKT–100xBA, x=0–0.10) ceramics were prepared by two-step sintering method and their phase structure, micro morphology and electrical properties were systematically investigated. X-ray diffraction analysis indicates a pure perovskite phase for x≤0.06 as well as a structural evolution from a tetragonal toward a pseudocubic phase. Transmission electron microscopy study of the x=0.04 composition reveals the existence of antiferroelectric phase with a⁰a⁰c⁺ oxygen octahedron tilting which is in the form of nano-domains. Polarization-electric field and current-electric field hysteresis loops demonstrate that the increase of BA concentration destroys the ferroelectric order and strengthens antiferroelectric order. A much enhanced energy storage density of 1.15 J/cm³ and efficiency of 73.2% is achieved under 105 kV/cm at x=0.06. In addition, its energy storage property is found to depend weakly on temperature within the measurement range of 25–150 °C.     

Effect of Sn:Ti variations on electric filed induced AFE–FE phase transition in PLZST antiferroelectric ceramics

The effect of Sn:Ti variations on antiferroelectric to ferroelectric phase transition of (Pb_0.97La_0.02)(Zr_0.65Sn_0.35?xTi_x)O₃ (x = 0.08–0.11) ceramics with compositions near antiferroelectric to ferroelectric morphotropic phase boundary was studied. X-ray diffraction showed that all samples were tetragonal phase at room temperature. With the increase of x from 0.08 to 0.1, all samples showed the typical antiferroelectric double loops. The critical value E_AF of the electric-field induced antiferroelectric to ferroelectric phase transition decreased from 64 kV/cm to 38 kV/cm, and the electric field E_FA of induced-ferroelectric to antiferroelectric phase transition decreased from 44 kV/cm to 10 kV/cm. A high polarization of the sample with x = 0.1 can be induced with a lower electric filed. The variations of Sn:Ti ratio had no effect on hysteresis of ΔE (=E_AF ? E_FA), but ΔE reduced with temperature increasing. The virgin sample of which x = 0.11 was intrinsic antiferroelectric phase, but the remanent polarization of induced-ferroelectric phase remained after electric-field was removed at room temperature.     

Lead-free BaTiO3-Bi0.5Na0.5TiO3-Na0.73Bi0.09NbO3 relaxor ferroelectric ceramics for high energy storage

A series of (1-x)(0.65BaTiO₃-0.35Bi_0.5Na_0.5TiO₃)-xNa_0.73Bi_0.09NbO₃ ((1-x)BBNT-xNBN) (x = 0–0.14) ceramics were designed and fabricated using the conventional solid-state sintering method. The microstructure, dielectric property, relaxor behavior and energy storage property were systematically investigated. X-ray diffraction results reveal a pure perovskite structure and dielectric measurements exhibit a relaxor behavior for the (1-x)BBNT-xNBN ceramics. The slim polarization electric field (P-E) loops were observed in the samples with x ≥ 0.02 and the addition of Na_0.73Bi_0.09NbO₃ (NBN) could decrease the remnant polarization (P_r) of the (1-x)BBNT-xNBN ceramics obviously. The sample with x = 0.08 exhibits the highest energy storage density of 1.70 J/cm³ and the energy storage efficiency of 82% at 172 kV/cm owing to its submicron grain size and high relative density. These results show that the (1-x)BBNT-xNBN ceramics may be promising lead-free materials for high energy storage density capacitors.     

Effects of Sr substitution for Ba on dielectric and energy-storage properties of SrO-BaO-K2O-Nb2O5-SiO2 glass-ceramics

In this work, [xSrO, (1 − x)BaO]-K₂O -Nb₂O₅-SiO₂ (SBKNS, x = 0.2, 0.4, 0.6, 0.8) glass-ceramics were synthesized through the controlled crystallization method. The phase structure, dielectric and energy-storage properties were systematically studied through the Sr substitution for Ba. It was found that the dielectric properties were improved due to the formation of solid liquid phase Sr_0.5Ba_0.5Nb₂O₆. Breakdown strength firstly increases and then decreases, which strongly depends on the variation in interfacial polarization. The highest value of breakdown strength reaches 1828 ± 88 kV/cm for x = 0.4, which is attributed to more uniform and dense microstructure and lower interfacial polarization. Correspondingly, the optimized theoretical energy-storage density reaches up to 17.45 ± 0.74 J/cm³. The maximum of discharged energy-storage density of 1.45 J/cm³ from P-E loop was acquired under electric field of 500 kV/cm. Moreover, discharged power density of the capacitor was evaluated and reached a high value of 1.76 MV/cm³ in pulsed charged-discharged circuit.     

Enhanced electrocaloric effect and energy-storage performance in PBLZT films with various Ba2+ content

(100)-oriented Pb_(0.90−x)Ba_xLa_0.10Zr_0.90Ti_0.10O₃ (x=0, 0.02, 0.05 and 0.11) antiferroelectric thick films were deposited on LaNiO₃/Si (100) substrates by the sol-gel process. The influences of Ba²⁺ content on the dielectric properties, electrocaloric effect (ECE), energy-storage performance and leakage current were systematically investigated. With Ba²⁺ content increasing, the temperature (T_m) corresponding to the maximum dielectric constant of the thick films was decreased, while their diffuseness was increased. The maximum ECE ∆T=18.1 °C was obtained in the thick film with x=0.05 at room temperature under ∆E=700 kV/cm. The maximum energy storage density of 42.3 J/cm³ and the corresponding efficiency of 68% was achieved in the film with x=0.11, companied by a power density of 0.53 MW/cm³, due to its high breakdown strength. In addition, a small leakage current density (<10⁻⁵ A/cm²) were attained in these films at room temperature. In conclusion, we believe that this kind of antiferroelctric thick film is a potential candidate for applications in solid cooling devices and the energy-storage systems.     

PLZST antiferroelectric ceramics with promising energy storage and discharge performance for high power applications

Capacitors are widely used as energy storage elements in electric vehicles (EVs) and pulsed power. At present, it is still challenging to develop capacitor dielectrics with good energy storage and discharge performance. In this work, antiferroelectric (AFE) ceramics (Pb_0.94La_0.04)[(Zr_0.6Sn_0.4)_0.92Ti_0.08]O₃ with enhanced antiferroelectricity were fabricated by a rolling process. The obtained ceramics have a high recoverable energy density of 5.2 J/cm³ and an extremely high efficiency of 91.2% at 327 kV/cm. The ceramics have good energy storage and discharge performance in the temperature range from −40°C to 100°C due to the existence of AFE phase. An energy density of 3.7 J/cm³ can be released at 200 kV/cm in less than 500 ns and the discharge current keeps stable after 1000 charge-discharge cycles. By direct short experiment, a current density of 1657 A/cm², which is the highest result in recently developed AFE ceramics, and a power density of 228 MW/cm³ were achieved. The possibility of using AFEs at low temperature was confirmed. The excellent energy storage and discharge performance prove the great potential of the obtained ceramics in high energy and power density applications.     

Excellent energy storage performance of NaNbO3-based antiferroelectric ceramics with ultrafast charge/discharge rate

Dielectric capacitors have drawn increasing attention due to their fast charge/discharge rates and high power density. Among all known ceramic dielectric materials, antiferroelectrics are more attractive for their unique double ferroelectric hysteresis loops and higher energy densities. Here, a series of antiferroelectric ceramics x(0.95Bi_0.5Na_0.5TiO₃-0.05SrZrO₃)-(1-x)NaNbO₃ (xBNTSZ-(1-x)NN, x = 0.23, 0.30, 0.35, 0.50) have been prepared. By stabilizing the antiferroelectric phase and postponing the critical electric field of the antiferroelectric-ferroelectric phase transition, an impressive discharge energy storage density of 4.08 J/cm³ at a breakdown strength of 370 kV/cm was achieved for the 0.35BNTSZ-0.65 N N. A superior comprehensive performance for the 0.50BNTSZ-0.50 N N ceramic with a discharge energy storage density (W_dis) of 3.78 J/cm³ and an efficiency of 86 % at an electric field strength of 320 kV/cm along with excellent frequency, temperature, and fatigue stabilities (fluctuations of W_dis≤±5% within 0.01∼100 Hz, W_dis≤10 % over 20∼140 °C, and W_dis≤1% over 10⁶ cycle numbers) is realized. Furthermore, 0.50BNTSZ-0.50 N N ceramics simultaneously exhibit a high current density (622.5 A/cm²), high power density (112 MW/cm³), and fast discharge rate (t = 47 ns), all of which make it an excellent candidate for the pulsed power devices.     

Microstructure and electrical properties of Mn/Y codoped Ba0.67Sr0.33TiO3 ceramics

Pure and Mn/Y codoped Ba_0.67Sr_0.33TiO₃ (BST) ceramics were fabricated via the citrate–nitrate combustion technique, and the microstructure and electrical properties of BST ceramics were mainly investigated. The Mn/Y codoping concentration has a strong influence on the microstructure and electrical properties of BST ceramics. All BST ceramics possess a pure polycrystalline structure. The density, dielectric loss, leakage current, and ferroelectric properties are improved by codoping 0.5 mol% Mn and 1.0 mol% Y to BST. The relative density of 0.5 mol% Mn/1.0 mol% Y-codoped BST (BST0510) ceramics reaches 97.5% of the theoretical value. BST0510 ceramics have the lowest dielectric loss (tanδ < 0.0073 at 1 kHz) among all BST ceramics. BST0510 ceramics also demonstrate a low leakage current density (1.23 × 10^?7 A/cm²) at an applied field of 10 kV/cm, and excellent ferroelectric properties with a remanent polarization of 2P_r = 15.327 μC/cm² and a coercive field of 2E_c = 3.456 kV/cm. Therefore, the Mn and Y with optimum content help improve the electrical properties of BST materials.     

Effect of SiO2 additive on dielectric response and energy storage performance of Ba0.4Sr0.6TiO3 ceramics

SiO₂-added barium strontium titanate ceramics Ba_0.4Sr_0.6TiO₃-xwt%SiO₂ (x=0, 0.5, 1, 3, BSTSx) were prepared via a traditional solid state reaction method. The effect of SiO₂ additive on the microstructure, dielectric response and energy storage properties was investigated. The results confirmed that with the increase of SiO₂ additive, diffuse phase transition arises and the dielectric constant decreases. An equivalent circuit model and Arrhenius law were used to calculate the activation energy of grain and grain boundary, which indicated that the dielectric relaxation at high temperature was caused by oxygen vacancy. While appropriate SiO₂ additive led to improve the breakdown strength, further increase of SiO₂ deteriorated the energy storage because of the low densification. Finally, optimized energy storage performance was obtained for BSTS0.5 ceramics: dielectric constant of 1002, dielectric loss of 0.45%, energy density of 0.86 J/cm³ and energy storage efficiency of 79% at 134 kV/cm.     

Enhanced energy storage properties of {Bi0.5[(Na0.8K0.2)1-zLiz]0.5}0.96Sr0.04(Ti1-x-yTaxNby)O3 lead-free ceramics

Energy storage properties of {Bi_0.5[(Na_0.8K_0.2)_1-zLi_z]_0.5}_0.96Sr_0.04(Ti_1-x-yTa_xNb_y)O₃ (BNKLSTTN-x/y/z) lead-free ceramics are investigated. It is found that Ta performs better than Nb in the case of their energy storage density values, and the addition of optimum Li contents can enhance the energy storage properties by enhancing the dielectric breakdown strength (DBS). Enhanced energy storage density of 1.60 J/cm³ under a low electric field of 90 kV/cm is achieved in BNKLSTTN-0.025/0/0.10 samples, and the fatigue-free properties are also observed. In addition, the BNKLSTTN-0.025/0/0.10 samples show the enhanced temperature dependence of energy storage density. These results indicate that the BNKLSTTN-x/y/z ceramics are one of the most promising lead-free materials for energy storage applications.     

Influence of Ca substitution on microstructure and electrical properties of Ba(Zr,Ti)O3 ceramics

In the present work, lead-free (Ba_1?xCa_x)(Zr_0.04Ti_0.96)O₃ (x=0.00–0.09) ceramics were fabricated via a solid-state reaction method. The microstructure and electrical properties of the ceramics were investigated. The microstructure of the BCZT ceramics showed a core shell structure at compositions of x=0.03 and 0.06. The substitution of small amount of Ba²⁺ by Ca²⁺ resulted in an improvement of the piezoelectric, dielectric and ferroelectric properties of the ceramics. The orthorhombic–tetragonal phase transition was found in the composition of x≤0.03. Piezoelectric coefficient of d₃₃～392 pC/N and lowest E_c～3.3 kV/cm with highest P_r～14.1 μC/cm² were obtained for the composition of x=0.03 while its Curie temperature (T_C) was as high as 125 °C. However, the ferroelectric to paraelectric transition temperature had slightly shifted towards room temperature with increasing Ca²⁺ concentration.     

Antiferroelectricity in tantalum doped (Bi0.5Na0.5)0.94Ba0.06TiO3 lead-free ceramics

(Bi_0.5Na_0.5)_0.94Ba_0.06(Ti_1−xTa_x)O₃ (x=0.00–0.04) lead-free polycrystalline ceramics were synthesized using the solid state reaction route, and their crystal structures and electrical properties were systematically studied. With the introduction of Ta substitution, the relaxor antiferroelectric phase with tetragonal P4bm symmetry is stabilized. The representative double polarization hysteresis loops and sprout shaped strain curves for antiferroelectric ceramics are observed at higher Ta contents with x=0.01–0.02 at room temperature. x=0.01 shows the largest strain of 3.81‰ under 60 kV/cm, indicating a good candidate for actuator applications. The polarization and strain hysteresis loops are also evaluated to verify the temperature-induced normal ferroelectric phase to relaxor antiferroelectric phase transition at temperature up to 120 °C. The energy storage density and efficiency at various temperatures are calculated and analyzed in the compositions of x=0.00–0.02. The results indicate that the energy storage density becomes more temperature independent with the increase of Ta concentration, which are promising for applications in high-temperature capacitors.     

Energy storage density and tunable dielectric properties of BaTi0.85Sn0.15O3/MgO composite ceramics prepared by SPS

(100-x) wt.% BaTi_0.85Sn_0.15O₃–x wt.% MgO (BTS/MgO) composite ceramics were prepared by spark plasma sintering (SPS) technology. Phase constitution, microstructure, dielectric and electrical energy storage properties of BTS/MgO composite ceramics were investigated. The samples prepared by SPS had smaller grain size and presented layer-plate substructure. Dielectric permittivity and dielectric loss of BTS/MgO composite ceramics decreased significantly with the content of MgO increasing, and dielectric tunability maintained a relatively high value (>45%). Meanwhile, the dielectric breakdown strength was improved when addition of MgO in BTS matrix, which resulted in a significant improvement of energy storage density. The high dielectric breakdown strength of 190 kV/cm, energy storage density of 0.5107 J/cm³ and energy storage efficiency of 92.11% were obtained in 90 wt.% BaTi_0.85Sn_0.15O₃–10 wt.% MgO composite ceramics. Therefore, BTS/MgO composites with good tunable dielectric properties and electrical energy storage properties could be exploited for energy storage and phase shifter device applications.     

Low temperature fabrication of lead-free KNN-LS-BS ceramics via the combustion method

Lead-free piezoelectric 0.992(0.95K_0.5Na_0.5NbO₃–0.05LiSbO₃)–0.008BiScO₃; KNN-LS-BS ceramics were successfully prepared using the combustion method. The highest % perovskite phase was found in the sample calcined at 700 °C for 1 h. The structural phase of orthorhombic structure was also detected in this sample. For the sintered ceramics, a pure tetragonal perovskite phase was observed in the samples sintered between 1025 and 1100 °C. The microstructure of ceramics showed a square or rectangular shape and the average grain size increased with increasing of sintering temperature. The density of the ceramics increased with increasing of sintered temperature up to 1075 °C, were it reached 97.5% of theoretical density and then dropped in value when the sintered temperature further increased. The excellent electrical properties of ε_r at T_c=6600, tanδ at T_c=0.04, P_r (at 40 kV/cm)=19.4 μC/cm² and E_c (at 40 kV/cm)=24.1 kV/cm were obtained in the most dense ceramic. The results indicate that the KNN-LS-BS ceramics are promising lead-free piezoelectric materials.     

High energy storage and ultrafast discharge in NaNbO3-based lead-free dielectric capacitors via a relaxor strategy

Dielectric capacitors with decent energy storage and fast charge-discharge performances are essential in advanced pulsed power systems. In this study, novel ceramics (1-x)NaNbO₃-xBi(Ni_2/3Nb_1/3)O₃(xBNN, x = 0.05, 0.1, 0.15 and 0.20) with high energy storage capability, large power density and ultrafast discharge speed were designed and prepared. The impedance analysis proves that the introducing an appropriate amount of Bi(Ni_0·5Nb_0.5)O₃ boosts the insulation ability, thus obtaining a high breakdown strength (E_b) of 440 kV/cm in xBNN ceramics. A high energy storage density (W_total) of 4.09 J/cm³, recoverable energy storage density (W_rec) of 3.31 J/cm³, and efficiency (η) of 80.9% were attained in the 0.15BNN ceramics. Furthermore, frequency and temperature stability (fluctuations of W_rec ≤ 0.4% over 5–100 Hz and W_rec ≤ 12.3% over 20–120 °C) were also observed. The 0.15BNN ceramics exhibited a large power density (19 MW/cm³) and ultrafast discharge time (~37 ns) over the range of ambient temperature to 120 °C. These enhanced performances may be attributed to the improved breakdown strength and relaxor behavior through the incorporation of BNN. In conclusion, these findings indicate that 0.15BNN ceramics may serve as promising materials for pulsed power systems.     

Relation between piezoelectric properties of ceramics and output power density of energy harvester

(1?x)Pb(Zr_0.47Ti_0.53)O₃–xPb[(Zn_0.4Ni_0.6)_1/3Nb_2/3]O₃ [(1?x)PZT–xP(ZN)N] ceramics with 0.26 ≤ x ≤ 0.31 were sintered at 1100 °C, and their energy harvesters were fabricated. All specimens exhibit a similar energy convergence efficiency. However, the transduction coefficient (d₃₃ × g₃₃) increased with x, reaching 21.5 × 10^?15 m²/N for the x = 0.31specimen; the figure-of-merit of the specimens shows a similar variation. The output energy density of the energy harvester also increased with x, and a high output energy density of 231 mW/cm³ was obtained for the harvester fabricated using the x = 0.31 specimen, indicating that the d₃₃ × g₃₃ value significantly affects the output energy density of the energy harvester.     

NaNbO3-based short-range antiferroelectric ceramics with ultrahigh energy storage performance

Lead-free NaNbO₃ (NN) antiferroelectric ceramics provide superior energy storage performance and good temperature/frequency stability, which are solid candidates for dielectric capacitors in high power/pulse electronic power systems. However, their conversion of the antiferroelectric P phase to the ferroelectric Q phase at room temperature is always accompanied with large remnant polarization (P_r), which significantly reduces their effective energy storage density and efficiency. In this study, to optimize the energy storage properties, short-range antiferroelectric (0.95-x)NaNbO₃-xBi(Mg_2/3Nb_1/3)O₃-0.05CaZrO₃ (xBMN) ceramics were designed to stabilize the antiferroelectric phase, in which the local random fields were simultaneously constructed. The results showed that the antiferroelectric orthorhombic P phase was transformed into the R phase, and the local short-range random fields were generated, which effectively inhibited the hysteresis loss and P_r. Of great interest is that the 0.12BMN ceramics displayed a large recoverable energy storage density (W_rec) of 5.9 J/cm³ and high efficiency (η) of 85% at the breakdown strength (E_b) of 640 kV/cm. The material also showed good frequency stability in the frequency range of 2–300 Hz, excellent temperature stability in the temperature range of 20–110 ℃, and a very short discharge time (t_0.9∼4.92 μs). These results indicate that xBMN ceramics have great potential for advanced energy storage capacitor applications.     

Crystal structure,microstructure and electrical properties of (1−x−y)Bi0.5Na0.5TiO3–xBi0.5K0.5TiO3–yBiFeO3 ceramics near MPB prepared via the combustion technique

(1?x?y)Bi_0.5Na_0.5TiO₃–xBi_0.5K_0.5TiO₃–yBiFeO₃ (BNKFT-x/y with 0.12≤x≤0.24, 0≤y≤0.07) lead-free piezoelectric ceramics have been prepared by the combustion technique. The effects of amounts of x and y on structures and electrical properties were examined. Powders and ceramics can be well calcined and sintered at 750 °C for 2 h and 1025–1050 °C, respectively. The results indicated that the crystalline structure and microstructure changed with the increase of x and y concentrations. XRD results of BNKFT-x/0.03 and BNKFT-0.18/y ceramics with 0.12≤x≤0.24 and 0≤y≤0.07 showed the rhombohedral–tetragonal morphotropic phase boundary (MPB). The addition of y caused a promoted grain growth while the addition of x suppressed the grain growth. The highest density (ρ=5.85 g/cm³), superior dielectric properties at T_c (ε_r=7846 and tan δ=0.02), remnant polarization measured at 40 kV/cm (P_r = 20.1 μC/cm²) and piezoelectric coefficient (d₃₃=213 pC/N) were obtained for x=0.18 and y=0.03.     

Ameliorative energy-storage properties stemmed from the refined grains in PBLZS antiferroelectric ceramics via introducing liquid phase sintering

The low breakdown strength (BDS) of antiferroelectric ceramics, which become failure before undergoing electrical field induced antiferroelectric-ferroelectric phase transition, have seriously restricted the progress of pulsed power capacitors. The method of refining grain sizes via the incorporation of glass additive is supposed to be an outstanding strategy to boost the BDS. Herein, the (Pb_0.91Ba_0.015La_0.05)(Zr_0.6Sn_0.4)O₃ (PBLZS) antiferroelectric ceramics with the introduce of BaO-B₂O₃-Al₂O₃-SiO₂ (BBAS) glass are designed and synthesized by a traditional solid-state reaction. When the glass content is 0.4 wt%, the recoverable energy storage density (W_rec) increases by 215 % from 2.0 J/cm³ to 6.3 J/cm³, together with a greatly enhanced BDS up to 390 kV/cm versus 270 kV/cm of pure ceramics. Meanwhile, the corresponding sintering temperature is remarkably decreased from 1300℃ to 1100℃. The superior charge and discharge performance can be obtained under the electrical field of 310 kV/cm, including a giant current density (1184.7 A/cm²), a high power density (184.2 MW/cm³), and an ultra-fast discharge period (40 ns). The prominent energy storage properties and low sintering temperature make it become a good candidate for fabricating multilayer pulsed power ceramic capacitors.