Ultrahigh energy storage density and efficiency in PLZST antiferroelectric ceramics via multiple optimization strategy

Antiferroelectric (AFE) ceramic materials possess ultrahigh energy storage density due to their unique double hysteresis characteristics, and PbZrO₃ is one of the promising systems, but previous materials still suffer from the problem that energy storage density and energy storage efficiency can hardly be improved synergistically. In this work, a multiple optimization strategy is proposed to substantially improve the energy storage efficiency while maintaining the high energy storage density of PZ-based AFE ceramics. Sr²⁺-doped (Pb_0.90La_0.02Sr_0.08)[(Zr_0.5Sn_0.5)_0.9Ti_0.1]_0.995O₃ ceramics was successfully synthesized by viscous polymer process and two-step sintering. The diffuse phase transition constructed in this ceramic depleted the threshold electric field hysteresis and current while the breakdown field strength was increased again. An ultrahigh recoverable energy density (W_rec) of 7.9 J/cm³ with a high energy storage efficiency (η) of 96.4 % are achieved synchronously at an electric field of 510 kV/cm. Moreover, the AFE ceramics possess remarkable discharge energy storage properties with a high discharge energy density (W_d) of 7.4 J/cm³ and a large power density (P_d) of 224 MW/cm³.     

Electric field tunable thermal stability of energy storage properties of PLZST antiferroelectric ceramics

The electrical hysteresis behaviors and energy storage performance of Pb_0.97La_0.02(Zr_0.58Sn_0.335Ti_0.085)O₃ antiferroelectric (AFE) ceramics were studied under the combined effects of electric field and temperature. It was observed that the temperature dependence of recoverable energy density (W_re) of AFE ceramics depends critically on the applied electric field. While W_re at lower electric fields (<8 kV/mm) shows increasing tendency with increasing temperature from 20°C to 100°C, W_re at higher electric fields (>8 kV/mm) demonstrates decreasing dependence. There exists an appropriate electric field (8 kV/mm) under which the AFE ceramics exhibit nearly temperature‐independent W_re (the variation is less than 0.5% per 10°C). The underlying physical principles were also discussed in this study. These results indicate that the temperature dependence of W_re of AFE materials can be tuned through selecting appropriate electric fields and provide an avenue to obtain thermal stable energy storage capacitors, which should be of great interest to modern energy storage community.     

Ultrahigh breakdown strength and energy density in PLZST@ PBSAZM antiferroelectric ceramics based on core-shell structure

A novel core-shell structured Pb_0.91La_0.06(Zr_0.552Sn_0.368Ti_0.08)O₃@PbO–B₂O₃-SiO₂-Al₂O₃-ZnO-MnO₂ ([email protected]) antiferroelectric particles were successfully fabricated via sol-gel method. As expected, the sintering temperature was notably reduced from 1250 ºC to 1100 ºC with the increasing glass contents. More importantly, the breakdown strengths of [email protected] ceramics were significantly increased from 252 kV/cm to 402 kV/cm. As a result, the energy density was up to 7.4 J/cm³ with 1 wt.% of coating glass content, a 55.3% enhancement over the pure PLZST (4.7 J/cm³). Furthermore, the simulations of electric field distribution provided a powerful evidence that the enhancement of the breakdown strength was induced by the core-shell structure, since the glass coating layer could not only undertake the most of electric field, but also impede the grain growth to achieve the smaller grains, which led to the reduction of electric field intensity on the grain cores.     

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

Featured with high polarization and large electric field-induced phase transition, PbZrO₃-based antiferroelectric (AFE) materials are regarded as prospective candidates for energy-storage applications. However, systematical studies on PbZrO₃-based materials are insufficient because of their complex chemical compositions and various phase structures. In this work, (Pb_0.94La_0.04)(Zr_1-x-ySn_xTi_y)O₃ (abbreviated as PLZST, 0 ≤ x ≤ 0.5, 0.01 ≤ y ≤ 0.1) AFE system was selected and the energy-storage behavior was regulated. It is found that low Ti content benefits to obtain satisfactory electric breakdown strength, realizing high energy-storage density. With Sn content increasing, the electric hysteresis decreases gradually, which is beneficial to improve energy conversion efficiency. As a result, a large recoverable energy-storage density of 9.6 J/cm³ and a high energy conversion efficiency of 90.2% were achieved in (Pb_0.94La_0.04)(Zr_0.49Sn_0.5Ti_0.01)O₃ ceramic. This work reveals energy-storage behavior of PLZST AFE materials systematically, providing reference for performance tailoring and new material designing in energy-storage applications.     

Large energy storage density,low energy loss and highly stable (Pb0.97La0.02)(Zr0.66Sn0.23Ti0.11)O3 antiferroelectric thin-film capacitors

In this work, high performance (Pb_0.97La_0.02)(Zr_0.66Sn_0.23Ti_0.11)O₃ polycrystalline antiferroelectric thin-film was successfully fabricated on (La_0.7Sr_0.3)MnO₃/Al₂O₃(0001) substrate via a cost-effectively chemical solution method. A large recoverable energy storage density (W_re) of 46.3?J/cm³ and high efficiency (η) of 84% were realized simultaneously under an electric field of 4?MV/cm by taking full advantage of the linear dielectric response after the electric field induced antiferroelectric-ferroelectric transition. Moreover, the PLZST thin-film displayed high temperature stability. With increasing temperature from 300?K to 380?K, the W_re decreased only 1.3%. The film also exhibited good fatigue endurance up to 1?×?10⁵ cycling under an electric field of 2.2?MV/cm. Our work underlines the importance of the interface quality between the film and the substrate and the important role of linear dielectric answer after saturation in the improvement of the energy storage density and efficiency of antiferroelectric materials.     

Low temperature sintering of PLZST-based antiferroelectric ceramics with Al2O3 addition for energy storage applications

Antiferroelectric (AFE) materials have superior energy storage properties in high power multilayer ceramic capacitors (MLCCs). To adapt to the sintering temperature of inner metal electrodes with less palladium content, in this work, Al₂O₃ was added to Pb_0.95La_0.02Sr_0.02(Zr_0.50Sn_0.40Ti_0.10)O₃ (PLSZST) AFE ceramics, in an attempt to reduce the sintering temperature. Results of this study demonstrate that the optimal composition of PLSZST-0.8 wt% Al₂O₃ sintered at a lower temperature 1040 ℃, has a high recoverable energy density (W_re, 3.23 J/cm³) and a high efficiency (η, 90 %) at room temperature. It is also high in pulse discharge energy density (W_dis, 2.45 J/cm³), current density (1369 A/cm²), and has an extremely short period of discharge (less than 500 ns). In addition, both W_re and η demonstrate a good stability in temperature within a wide range of 30 ℃-100 ℃. In sum, this novel AFE composition has great potentials for energy storage applications such as high energy density MLCCs.     

Achieving excellent energy storage density of Pb0.97La0.02(ZrxSn0.05Ti0.95-x)O3 ceramics by the B-site modification

The applications of antiferroelectric (AFE) materials in miniaturized and integrated electronic devices are limited by their low energy density. To address the above issue, the antiferroelectricity of the reinforced material was designed to improve its AFE-ferroelectric (FE) phase transition under electric fields. In this present study, the composition of Zr⁴⁺ (0.72 Å) and Ti⁴⁺ (0.605 Å) at B-site of Pb_0.97La_0.02(Zr_xSn_0.05Ti_0.95-x)O₃ ceramics with orthogonal reflections are synthesized via the tape-casting method. These ceramics are modified to enhance their antiferroelectricity by reducing their tolerance factor. A recoverable energy storage density W_rec 12.1 J/cm³ was obtained for x = 0.93 under 376 kV/cm, which is superior value than reported until now in lead-based energy storage systems. Moreover, the discharge energy density can reach 10.23 J/cm³, and 90 % of which can be released within 5.66 μs. This work provides a new window and potential materials for further industrialization of pulse power capacitors.     

Enhanced breakdown strength and energy density of antiferroelectric Pb,La(Zr,Sn,Ti)O3 ceramic by forming core-shell structure

Antiferroelectric Pb_0.97La_0.02(Zr_0.33Sn_0.55Ti_0.12)O₃@SiO₂ (with 5% mole of SiO₂) particles were synthesized by a citric acid sol-gel method. Transmission electron microscopy(TEM) results illustrated the formation of core–shell nanostructures with controllable shell thicknesses about 3–5?nm. X-ray diffraction(XRD) patterns displayed that a stable perovskite phase was preserved and no other crystallization peaks were discovered from the shell component. Scanning electron microscopy(SEM) and Energy Dispersive Spectrometer(EDS) investigations confirmed that core-shell structures were inherited from particles to ceramics after sintering. As a result, through the coating process, the breakdown strength of the ceramic increases by 95% from 12.2?kV/mm to 23.8?kV/mm and the recoverable energy density was greatly enhanced from 1.76?J/cm³ to 2.68?J/cm³. These results demonstrate a promising reaction method to enhance breakdown strength in antiferroelectrics for energy storage capacitor applications.     

Energy storage properties of NaNbO3-CaZrO3 ceramics with coexistence of ferroelectric and antiferroelectric phases

Anti-ferroelectric materials with large saturated polarization, small remnant polarization, and moderate breakdown strength are receiving increasing attention for modern high-power electrical systems. Here we demonstrated that by incorporating CaZrO₃ into NaNbO₃ ceramics, the antiferroelectricity in NaNbO₃-CaZrO₃ solid solutions could be stabilized at room temperature. The effects of phase constitution and microstructure on the dielectric properties, electrical breakdown strength, and energy storage properties of the NaNbO₃-CaZrO₃ ceramics were investigated. Ferroelectric and antiferroelectric phase coexistence in the NaNbO3-CaZrO₃ was confirmed by XRD and TEM analyses. With increasing CaZrO₃ content, the grain size was reduced, and the dielectric breakdown strength was improved. Therefore, a high energy density of 0.55?J/cm³ and efficiency of 63% was obtained in the NaNbO₃-0.04CaZrO₃ ceramics. These lead-free NaNbO₃-CaZrO₃ antiferroelectrics with good electrical energy storage can be exploited for high-power storage devices.     

Enhanced energy storage properties and stability in (Pb0.895La0.07)(ZrxTi1-x)O3 antiferroelectric ceramics

Recently, the (Pb,La)(Zr,Ti)O₃ antiferroelectric materials with slim-and-slanted double hysteresis loops have been widely drawn in the application of advanced pulsed power capacitors due to its low strain characteristic. In this work, the energy storage properties of (Pb_0.895La_0.07)(Zr_xTi_1-x)O₃ ceramics with different Zr contents are researched thoroughly because the substitution of Ti⁴⁺ by Zr⁴⁺ can reduce the tolerance factor t, enhancing the antiferroelectricity. The polarization-electric field hysteresis loops of the PLZT ceramics become slimmer with increasing Zr content. The highest recoverable energy storage density (W_re) of 3.38 J/cm³ and ultrahigh energy efficiency (η) of 86.5% are achieved in (Pb_0.895La_0.07)(Zr_0.9Ti_0.1)O₃ ceramic. The (Pb_0.895La_0.07)(Zr_0.9Ti_0.1)O₃ ceramic also hold fairly thermal stability (relative variation of W_re is less than 28% over 30 °C-120 °C), excellent frequency stability (10–1000 Hz) and good fatigue endurance. These results demonstrate that the (Pb_0.895La_0.07)(Zr_0.9Ti_0.1)O₃ ceramic can be a desirable material for dielectric energy storage capacitors, especially for pulse power technology.     

Enhanced the energy storage performance in AgNbO3‑based antiferroelectric ceramics via manipulation of oxygen vacancy

The applications of silver niobate (AgNbO₃)-based antiferroelectric (AFE) ceramics for potential energy storage are limited by the introduction of oxygen vacancies (OVs). The inevitable OVs narrow the band gap and promote grain growth, resulting in poor breakdown strength and low recoverable energy density (W_rec). Here, we report a significant energy density performance of (Ag_1–2xSr_x)(Nb_0.78Ta_0.22)O₃ AFE ceramics designed by restraining OVs. Electron paramagnetic resonance (EPR) and UVvis absorption spectra experiments demonstrate that the OV content gradually decreases and the band gap increases with increasing Sr content. Donor doping of Sr leads to the generation of silver ion vacancies, thus, the OV concentration decreases to maintain the electrical neutrality of the system. As a result, a high W_rec of ∼5.6 J/cm³ together with an energy efficiency of 70.1% at 300 kV/cm is achieved in the (Ag_0.92Sr_0.04)(Nb_0.78Ta_0.22)O₃ ceramic. This work offers a novel strategy for improving the energy storage properties of AgNbO₃-based AFE ceramics.     

Structure and energy storage performance of Ba-modified AgNbO3 lead-free antiferroelectric ceramics

The AgNbO₃ antiferroelectric (AFE) ceramics have attracted increasing attention for their high energy storage performance and environmentally friendly characters. In this work, Ag_1–2xBa_xNbO₃ ceramics were successfully prepared by the conventional solid-state reaction method. The effect of Ba-modification on phase structure, microstructure, and electric properties was systematically investigated. The introduction of Ba²⁺ ion led to complex cell parameter evolution and significant refinement of grain size. Room temperature dielectric permittivity increased obviously from ~260 for the pure AgNbO₃ counterpart to ~350 for those after adding a small amount of Ba element. Slim P-E hysteresis loops with improved AFE phase were achieved after Ba modification, due to the decrease of tolerance factor. A high recoverable energy density up to 2.3?J/cm³ with energy efficiency of 46% can be obtained for the composition of Ag_0.96Ba_0.02NbO₃, in correlation with the enhanced AFE stability, reduced P_r, increased P_m and decreased ΔE. Moreover, the Ag_0.96Ba_0.02NbO₃ ceramics also exhibited excellent temperature stability in both energy density and efficiency with small variation of <?5% over 20–120?℃. The results suggest that the electric properties of AgNbO₃ system can be largely tuned after Ba modification, making it a promising candidate for energy storage applications.     

Li+ and Sm3+ co-doped AgNbO3-based antiferroelectric ceramics for high-power energy storage

Ag_1-x-3yLi_xSm_yNbO₃ (x≤0.05, y≤0.05) (ALSN) antiferroelectric ceramics were successfully prepared via conventional solid-state reaction and sinter routes in oxygen atmosphere for improving the energy storage characteristic of pure AgNbO₃. The results indicate that all of the studied compositions display a pure orthorhombic antiferroelectric (AFE) perovskite structure, while their key parameters of electric-field-induced antiferroelectric-ferroelectric transition can be affected by Li⁺ or/and Sm³⁺ doping contents. The Sm³⁺ doping can enhance the stability of antiferroelectric state, giving rise to higher antiferroelectric-ferroelectric transition electric-field (E_F and E_B), while Li⁺ doping can reduce E_F and E_B for Sm³⁺ doped AgNbO₃ with low Sm³⁺ content (y≤0.03). When co-doping the same amounts of Li⁺ and Sm³⁺ at x=y≤0.03, both E_F and E_B almost remain unchanged. At x=y=0.05, the diffuse phase transition (DPT) behavior of antiferroelectric-paraelectric (AFE-PE) phase transition occurred, resulting in a “slim-like” double-polarization hysteresis with significantly enhanced E_F. Due to these features, both W_rec and η are improved compared with pure AgNbO₃. The W_rec and η with composition at x=y=0.05 is 2.33 J/cm³ and 58% under applying electric field of 240 kV/cm, respectively. The results suggest that building DPT behavior of AFE-PE phase transition could be an alternative strategy to improve the energy storage characteristic of AgNbO₃.     

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.     

High energy-storage performance of lead-free AgNbO3 antiferroelectric ceramics fabricated via a facile approach

AgNbO₃ lead free AFE ceramics are considered as one of the promising alternatives to energy storage applications. In the majority of studies concerning the preparation of AgNbO₃ AFE ceramics, an oxygen atmosphere is required to achieve high performance, increasing the complexity of the fabrication process. Herein, a facile approach to preparing AgNbO₃ ceramics in the ambient air was reported, in which the AgNbO₃ ultrafine powder with stable perovskite structure was synthesized by hydrothermal method instead of the conventional ball milling process, leading to a lower temperature of phase formation and thus smaller grain size. The resulting ceramics sintered at 940 °C displayed high breakdown strength (216 kV/cm) and a recoverable energy density of 3.26 J/cm³ with efficiency of 53.5 %. Also, the high thermal stability of recoverable energy density (with minimal variation of ≤20 %) and efficiency (≤ 10 %) over 30–150℃, enables AgNbO₃ ceramics achieved to be a promising candidate for energy storage applications.     

Enhanced energy storage density in Ca and Ta co-doped AgNbO3 antiferroelectric ceramics

Ca and Ta co-doped AgNbO₃ antiferroelectric lead-free ceramics were fabricated by rolling process technique, and improved energy storage properties were obtained. X-ray diffraction and Raman spectra indicate a single perovskite structure for (Ag_1-2xCa_x)(Nb_1-xTa_x)O₃ ceramics. The dielectric performances were also investigated, showing that increasing the content of Ca and Ta from 0.1 to 5 mol% gradually decreased the temperatures of the phase transition of monoclinic M₁-M₂ and M₂-M₃. This proved the enhanced antiferroelectricity stability associated with the enlarged low temperature phase transition region. The obtained (Ag_0.90Ca_0.05)(Nb_0.95Ta_0.05)O₃ ceramics exhibit an enhanced recoverable energy storage density (3.36 J/cm³) and efficiency (58.3%) with good temperature and frequency stability. The same composition shows excellent charge and discharge properties with a discharge current as high as 91.5 A and fast discharge speed (150 ns discharge period). All these merits demonstrate that AgNbO₃-based antiferroelectric ceramics are competitive with other lead-based and lead-free dielectric capacitors, which are promising candidates for dielectric energy storage applications.     

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 performances of Bi(Ni1/2Sb2/3)O3 added NaNbO3 relaxor ferroelectric ceramics

In the development of dielectric ceramic materials, the requirements of miniaturization and integration are becoming increasingly prominent. How to obtain greater capacitance in a smaller volume is one of the important pursuits. In this paper, lead-free (1-x)NaNbO₃-xBi(Ni_1/2Sb_2/3)O₃(xBNS) with high recoverable energy storage density (W_rec) and relatively high energy storage efficiency(η) were prepared by a solid state sintering method. Bi(Ni_1/2Sb_2/3)O₃ was introduced into the Sodium niobate ceramics(NN)-based ceramics to reduce the sintering temperature and increase the maximum breakdown field strength (E_b). Finally, 0.15BNS achieved a high E_b of 460 kV/cm, W_rec of 3.7 J/cm³ and η of 77%. In addition, the sample maintained excellent stability in the frequency range of 1–120 Hz. And the 0.15BNS ceramics also exhibited high power density (P_D = 36.4 MW/cm³), large current density (C_D = 520.8 A/cm²) and relatively fast charge-discharge rate (t_0.9 = 1050 ns). These results demonstrate the potential application value of xBNS ceramics in energy storage capacitors.     

Energy storage and release properties of Sr-doped (Pb,La)(Zr,Sn,Ti)O3 antiferroelectric ceramics

Pb_0.94−xLa_0.04Sr_x[(Zr_0.6Sn_0.4)_0.84Ti_0.16]O₃ (x=0,0.02,0.04,0.06) antiferroelectric ceramics were fabricated via conventional solid-state reaction. The increase of Sr content enhanced the stability of antiferroelectric phase, which resulted in the rise of phase transition fields and energy density. When x=0.06, the releasable energy density was 1.52 J/cm³ and the efficiency was 93.3% under 129 kV/cm. The pulsed discharge current was also measured to evaluate the energy release properties. Under 129 kV/cm, the obtained current density could be as high as 165.5 A/cm². The pulsed discharge energy density was 1.21 J/cm³ and 90% of that could be released in less than 200 ns. The high energy density, high efficiency and fast energy release time indicate that the obtained AFE ceramics are very promising for pulsed power capacitors.     

Antiferroelectric-liner dielectric solid solutions leading to large energy density and ultrahigh efficiency in PBLZST-CZT ceramics

A novel strategy to improve the energy-storage density and efficiency of the antiferroelectric (Pb_0.93Ba_0.04La_0.02)(Zr_0.65Sn_0.3Ti_0.05)O₃ (PBLZST) ceramics is presented by forming ceramic solid solutions. The introduction of linear dielectric Ca(Zr_0.5Ti_0.5)O₃ into PBLZST can effectively increase the breakdown strength, the antiferroelectric-to-ferroelectric phase transition field (E_F) and the ferroelectric-to-antiferroelectric phase transition field (E_A), while decreasing ΔE = E_F - E_A and the dielectric loss. This novel strategy leads to an ultrahigh efficiency of 94% and a remarkably high density of 4.14 J/cm³ in the PBLZST-based ceramics. The fundamental origins of high energy-storage density and efficiency are attributed to the enhanced tolerance factor and electronegativity difference in the complex perovskite structure, as well as the linear dielectric properties of Ca(Zr_0.5Ti_0.5)O₃. Our results qualify the antiferroelectric PBLZST ceramics as innovative and promising candidate for energy storage applications. Furthermore, it points out an effective approach to achieve high efficiency in antiferroelectric by forming ceramics with linear dielectric.