Enhanced energy storage properties and superior thermal stability in SNN-based tungsten bronze ceramics through substitution strategy

Tungsten bronze ceramics of composition Sr₂Ag_0.2Na_0.8Nb_5-xTa_xO₁₅ were synthesized by solid state methods to investigate the impact of Ta replacement on the structure and energy-storage properties (ESP). The study on the relationship between structure and electric properties revealed three main conclusions: (1) as the Ta⁵⁺ concentration increased, the crystal structure transformed from an orthorhombic Im2a phase to a tetragonal paraelectric P4bm phase; (2) a high recoverable energy storage density (1.44 J/cm³) and a moderate efficiency (82%) under low-electric fields was obtained in x = 0.3 sample; (3) both dielectric properties (?9.6 to 232.7 °C) and ESP (30–150 °C) exhibit an excellent thermal stability for x = 0.3 sample. In addition, a high current density (863.69 A/cm²) and a large powder density (70.21 MW/cm³) were achieved simultaneously. The current system could be a promising candidate in temperature-stable dielectric capacitors under low-fields and over a broad temperature range.     

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.     

Thermal stability of dielectric and energy storage performances of Ca-substituted BNTZ ferroelectric ceramics

In this study, we synthesized [Ca_x(Bi₀.₅Na_0.5)_1?x](Ti₀₈₅Zr_0.15)O₃ (Ca-substituted BNTZ) ferroelectric ceramics with x = 0–0.15 using a solid-state reaction technique. The structural evolution of Ca-substituted BNTZ was revealed by X-ray diffraction combined with Rietveld crystal structure refinement. A pseudocubic structure with P4bm symmetry is suggested for all Ca-substituted BNTZ samples. Temperature-dependent dielectric properties show a clear and broad dielectric peak of approximately 340 °C. The dielectric peak becomes even wider, and the thermal stability of the permittivity is dramatically improved when x gradually increases. In the x = 0.10 composition, the permittivity at 25–450 °C varies between +5% and ?14.5%. A recoverable energy storage density (W_rec) of 2.79 J/cm³ with an energy storage efficiency (η) of 76% was achieved in the x = 0.07 composition, which suggests superior properties over other BNT-based systems. In addition, the compositions of x = 0.07, 0.10 and 0.15 show excellent thermal stability of W_rec and η. This work proves that the thermal stability of dielectric and energy storage performances in BNT-based ferroelectric ceramics can be achieved by introducing ions without contributing to the polarization.     

Large energy storage density in BiFeO3-BaTiO3-AgNbO3 lead-free relaxor ceramics

Lead-free (0.70-x)BiFeO₃-0.30BaTiO₃-xAgNbO₃+5‰mol CuO (abbreviated as BF-BT-xAN) ceramics were fabricated using a modified thermal quenching technique. BF-BT-xAN ceramics are of a perovskite structure with morphotropic phase boundary (MPB) and show strong relaxor properties. Remarkably, the high recoverable energy storage density of 2.11 J/cm³ is obtained for BF-BT-xAN with x = 0.14. For the x = 0.14 ceramics, its energy storage efficiency is as high as 84 % at relative low field of 195 kV/cm, together with an outstanding thermal stability in a broad temperature range from 25 °C to 150 °C. In addition, this ceramic maintains superior energy storage performance even after 8 × 10⁴ electrical cycles due to its high densification after doping Ag₂O and Nb₂O₅. The result suggests that lead-free BF-BT-xAN ceramics may be promising candidate for dielectric energy storage application.     

(1-x)Bi0.5Na0.47Li0.03TiO3-xNaNbO3 lead-free ceramics with superior energy storage performances and good temperature stability

Dielectric capacitors show great potential in superior energy storage devices. However, the energy density of these capacitors is still inadequate to meet the requirement of energy storage applications. In this study, the Bi_0.5Na_0.47Li_0.03TiO₃-xNaNbO₃ (BNLT-xNN) ceramics were prepared via conventional solid-phase reaction. Results showed that NN can efficaciously enhance the breakdown strength (E_b) and the relaxation behavior of the BNLT ceramic because of the broken ferroelectric long-range order. When x = 0.3, the maximum E_b reached 350 kV/cm, at which the 0.7BNLT-0.3NN ceramic exhibited the high recoverable energy storage density (W_rec) of 4.83 J/cm³ and great efficiency (η) of 78.9%. The ceramic demonstrated good temperature stability at 20 °C-160 °C and excellent fatigue resistance. Additionally, the 0.7BNLT-0.3NN ceramic presented high power density (P_D; ～77.58 MW/cm³), large current density (C_D; ～861.99 A/cm²), and quite short discharge time (t_0.9; ～0.090 μs). These results indicated that the 0.7BNLT-0.3NN material has excellent energy storage properties and various application prospects.     

Preparation and thermal shock resistance of anorthite solar thermal energy storage ceramics from magnesium slag

Anorthite solar thermal energy storage ceramics were fabricated from magnesium slag solid waste by pressureless sintering. The effects of CaO/SiO₂ ratio and sintering temperature on the physical, chemical, and thermophysical properties of ceramics were explored. X-ray diffraction results demonstrated that thermal shock process contributed to the formation of anorthite, and increasing CaO/SiO₂ ratio promoted the transformation of anorthite (CAS₂) into melilite (C₂AS). Some micro-cracks were found according to SEM analysis, forming by the mismatch of thermal expansion coefficients among phases. The combined effects of the low thermal expansion coefficient of anorthite and micro-crack toughing endowed the ceramic with good thermal shock resistance. Optimum comprehensive performances were observed in the sample with a CaO/SiO₂ ratio of 0.58 sintered at 1160°C, of which the specific thermal storage capacity was 0.63 J·g^-1·°C^-1(room temperature). The bending strength increased by 0.22% after 30 thermal shock times (room temperature-800°C, wind cooling). Therefore, the anorthite ceramics exhibited great potential for solar thermal energy storage.     

Y doping and grain size co-effects on the electrical energy storage performance of (Pb0.87Ba0.1La0.02) (Zr0.65Sn0.3Ti0.05)O3 anti-ferroelectric ceramics

(Pb_0.87Ba_0.1La_0.02) (Zr_0.65Sn_0.3Ti_0.05)O₃+x mol% Y (PBLZST-x, x=0–1.25) anti-ferroelectric (AFE) ceramics have been prepared by the solid-state reaction process, and the effect of Y-doping on the microstructure and electrical properties has been investigated. When the Y content increases from 0 mol% to 1.25 mol%, the average grain size of the PBLZST ceramics decreases by more than 3 times (from 4.7 μm to 1.5 μm). The doping and grain size co-effects lead to a significant increase in the AFE-to-FE and FE-to-AFE phase transition electric field (E_F and E_A), and result in a decrease in the width of the double hysteresis loops. As the Y content increases from 0 mol% to 0.75 mol%, the E_F increases from 53 KV/cm to 83 KV/cm and the E_A increases from 35 KV/cm to 72 KV/cm. The large recoverable energy density of 2.75 J/cm³ and the high energy efficiency of 71.5% can be achieved when 0.75 mol% Y is doped. The results indicate that Y-doping is an effective method to modulate the average grain size and improve the energy storage performance of the PBLZST anti-ferroelectric ceramics.     

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.     

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 energy density and thermal stability in relaxor ferroelectric Bi0.5Na0.5TiO3-Sr0.7Bi0.2TiO3 ceramics

Sr_0.7Bi_0.2TiO₃ (SBT) was introduced into Bi_0.5Na_0.5TiO₃ (BNT) via a standard solid-state route to modulate its relaxation behaviour and energy storage performance. With increasing SBT content, the perovskite structure of BNT transforms from a rhombohedral phase to a weakly polarized pseudo-cubic phase, and the relaxation behaviour is enhanced. In particular, the E_DBS is improved from 120 kV/cm of BNT to 160 kV/cm of 0.6BNT-0.4SBT, which displays a large recoverable energy storage density (W_rec = 2.20 J/cm³), implying a large potential ability of energy storage for the 0.6BNT-0.4SBT ceramic. Moreover, both dielectric properties (28–326 °C) and energy storage properties (20–140 °C) exhibit a good thermal stability for the same 0.6BNT-0.4SBT composition. These characteristics suggest 0.6BNT-0.4SBT ceramic could be a promising candidate to be applied in a pulse power system over a broad temperature range.     

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

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

High thermal stability of energy storage density and large strain improvement of lead-free Bi0.5(Na0.40K0.10)TiO3 piezoelectric ceramics doped with La and Zr

Properties of lead-free Bi_0.5-xLa_xNa_0.40K_0.10Ti_0.98Zr_0.02O₃ (x?=?0.000–0.040) ceramics were investigated. All ceramics have a pure perovskite structure. A high energy storage density (～1.00?J/cm³) at room temperature (RT) is noted for the x?=?0.030 sample, while x?=?0.020 and 0.040 samples have very high thermal stability of energy storage density of ～3% (at 75–150?°C). Furthermore, the x?=?0.030 and 0.040 samples have the highest energy storage efficiency (η) value of 94% at 125?°C with high thermal stability (η?=?84–95% at 25–150?°C). The x?=?0.005 sample has high electric field-induced strain (S_max?=?0.42%) and high normalized strain coefficient (d^*₃₃?=?S_max/E_max?=?700?pm/V) with large improvements (～200% and 163% for S_max and d^*₃₃, respectively), as compared to the based composition. This ceramic system has potentials for piezoelectric and/or energy storage density applications.     

A dispersed polycrystalline phase boundary constructed in CaZrO3 modified KNN based ceramics with both excellent piezoelectric properties and thermal stability

In this paper, the ceramics with composition of (0.98-x)(K_0.5Na_0.5)(Nb_0.96Sb_0.04)O₃-0.02(Bi_0.5Na_0.5)(Zr_0.8Ti_0.2)O_3-xCaZrO₃ (abbreviated as (0.98-x)KNNS-0.02BNZT-xCZ, x = 0, 0.01, 0.015, 0.02, 0.025, 0.03) were prepared by a traditional solid-state reaction method. The effect of the additional amount of CaZrO₃ on the phase structure, microstructure, dispersion index, domain structure and piezoelectric properties of ceramics was systematically studied. Finally, the piezoelectric properties and thermal stability of ceramics could be controlled by adding different amounts of CaZrO₃. The addition of CaZrO₃ transferred the phase structure of the ceramics from orthogonal-tetragonal (O-T) coexistence phase to rhombohedral-orthogonal (R–O) coexistence phase, which could be demonstrated by XRD test, temperature-dependent Raman spectra and ε_r‐T plot analysis. And when x = 0.02, the ceramics possessed the best piezoelectric and dielectric properties (d₃₃ = 253 pC/N, ε_r = 1185, tanδ = 0.044). Such excellent electrical properties could be originated from the heterogeneous domain structure and small-size nano-domains of the ceramics. Moreover, with the increase of CaZrO₃ doping amount, the dispersion index of ceramics gradually increased from 1.404 to 1.871, which showed more obvious dispersion phase transition characteristics and improved the thermal stability of ceramics. Particularly, when x = 0.02, after annealing at a high temperature of 220 °C (close to its Curie temperature), the d₃₃ tested at room temperature remained above 85% of that without annealing. The results indicated that (0.98-x)KNNS-0.02BNZT-xCZ ceramic was a promising lead-free piezoelectric ceramic system.     

An effective strategy to realize superior high-temperature energy storage properties in Na0.5Bi0.5TiO3 based lead-free ceramics

To develop and fabricate environmentally friendly dielectric capacitors used in high-temperature environment, in this work, we prepare La³⁺ doped 0.94Na_0.5Bi_0.5TiO₃-0.06BaTiO₃ lead-free relaxor ferroelectric ceramics with high and wide phase transition temperature. With the introduction of La³⁺, due to the enhancement of the A- and B- site cation ion disorder, the dielectric relaxation characteristics of the ceramics are more obvious. Therefore, the polarization-electric field loops become slimmer and the remnant polarization (P_r) reduces. In addition, because La³⁺ as a donor dopant has lower mobility than A-site cation ions in the ceramic matrix, the grain sizes decrease with increasing La³⁺ content, which significantly leads to an increase in the breakdown strength (E_b). As a result, both a large recoverable energy density (W_rec) of 1.92 J/cm³ and a high energy efficiency (η) of 85.7% are obtained in the ceramic with 12 mol% La³⁺ content. More importantly, even at 200 °C and a low driving electric field of 155 kV/cm, the W_rec and η of this kind of ceramic are still as high as 1.2 J/cm³ and 89.4%, indicating good temperature stability. This work provides an effective and simple way to prepare environmentally friendly dielectric capacitors that are applicable in high-temperature environment.     

固-固相变储热材料的研究进展

与固-液相变材料相比,固-固相变材料（SS-PCMs）受到的关注较少;鉴于SS-PCMs具有储能密度高、无毒且腐蚀性小、相变时无液体产生且体积变化较小、不易发生相分离以及过冷度小等优点,因而是一类具有发展潜力的相变材料。本文基于SS-PCMs的研究现状,对近年来几类重要SS-PCMs如多元醇SS-PCMs、高分子类SS-PCMs及无机盐类SS-PCMs的研究进展进行了综述。简要阐述了SS-PCMs的分类以及各类SS-PCMs的性能、相变储热机制和优缺点。同时介绍了选择固-固相变材料应用时的基本原则,并针对相变材料热导率低,过冷度大、稳定性差等问题的改性研究进行了综述,还简要综述了SS-PCMs的应用研究。最后指出,未来的研究应着眼于解决已合成SS-PCMs的缺陷,开发多功能的SS-PCMs,并在SS-PCMs的实际应用方面实现突破。     

Low-temperature thermal energy storage with polymer-derived ceramic aerogels

Thermal energy storage (TES) with phase change materials (PCMs) presents some advantages when shape-stabilization is performed with ceramic aerogels. These low-density and ultra-porous materials guarantee high energy density and can be easily regenerated through simple pyrolysis while accounting for moderate mechanical properties. However, the small pore size that typically characterizes these sorbents can hinder the crystallization of PCMs, slightly reducing the energy density of the stabilized compound. In this work, we present the use of polymer-derived mesoporous SiC and SiOC aerogels for the stabilization of polyethylene glycol and a fatty alcohol (PureTemp 23), having a melting temperature of 17 and 23°C, respectively. Their TES performances point out maximum thermal efficiency values of around 80%. These performances are discussed accounting for the results of thermogravimetric analysis, differential scanning calorimetry, and leaking tests.     

Enhanced energy storage performance in Na(1-3x)BixNb0.85Ta0.15O3 relaxor ferroelectric ceramics

High-performance lead-free dielectric containers have excellent energy storage performance such as higher power density and energy density. While being eco-friendly materials, lead-free dielectric materials are more suitable for pulse power systems than other dielectric materials. In this study, Ta⁵⁺and Bi³⁺ ions were introduced into the A site and B site of the NaNbO₃ matrix. The introduction of Bi³⁺ ions induced the formation of a vacancy in the A site, yielding Na_(1-3x)Bi_xNb_0.85Ta_0.15O₃ (NBNT, x = 0.05, 0.08, 0.11, 0.14) ceramics. The recoverable energy density (W_rec) and the energy storage efficiency (η) were highest for the Na_0.67Bi_0.11Nb_0.85Ta_0.15O₃ ceramic, with values of 3.37 J/cm³ and 89% respectively. Batteries employing the Na_0.67Bi_0.11Nb_0.85Ta_0.15O₃ ceramic achieved a current density of 830.4 A/cm², an energy density of 49.8 MW/cm³ and 60.2 ns discharge time. These results show that the Na_0.67Bi_0.11Nb_0.85Ta_0.15O₃ ceramic is an effective energy storage material with broad application prospects.     

High energy storage density realized in Bi0.5Na0.5TiO3-based relaxor ferroelectric ceramics at ultralow sintering temperature

The miniaturization and integration trend of electronic applications requires high energy storage performance, and the development of multilayer ceramic capacitors (MLCC) demands the compatibility between ceramic sintering temperature and co-firing temperature of metal electrodes. Herein, we obtained a high recoverable energy storage density and a low sintering temperature simultaneously in 0.5(Bi_0.5Na_0.5)TiO₃-0.5SrTiO₃-x mol% CuO (0.5BNT-0.5ST-x mol% CuO) via the combination of adding CuO sintering aid and citrate sol-gel synthesis method. The optimum sintering temperature decreases significantly from 1130 °C for x = 0 to 820 °C for x = 2.0. The ceramic of 0.5BNT-0.5ST-1.5 mol% CuO exhibits a large W_rec of 2.20 J/cm³ and η of 72.39% under 230 kV/cm. Furthermore, the same sample also possesses a large C_D of 1740.97 A/cm², an extremely high P_D of 139.28 MW/cm³ and an ultrafast discharge speed of 82 ns. These merits reveal that the ceramic of 0.5BNT-0.5ST-1.5 mol% CuO has great potential in practical MLCC production.     

Enhanced energy storage in temperature stable Bi0.5Na0.5TiO3-modified BaTiO3-Bi(Zn2/3Nb1/3)O3 ceramics

Recently, BaTiO₃-BiMeO₃ ceramics have garnered focused research attention due to their outstanding performance, such as thermal stability, energy efficiency and rapid charge-discharge behavior, however, a lower recoverable energy storage density (W_rec) caused by a relatively low P_max (<30 μC/cm²) mainly hinders practical applications. Herein, the energy density and thermal stability are improved by adding a tertiary component, i.e., Bi_0.5Na_0.5TiO₃, into BaTiO₃-BiMeO₃, resulting in xBi_0.5Na_0.5TiO₃-modified 0.88BaTiO₃-0.12Bi(Zn_2/3Nb_1/3)O₃ ceramics, with x = 0, 0.1, 0.2, 0.3 and 0.4, with superior dielectric properties and eco-friendly impact. Incorporating Bi_0.5Na_0.5TiO₃ with a high saturation polarization and Curie temperature not only significantly enhances P_max of BaTiO₃-Bi(Zn_2/3Nb_1/3)O₃ but also improves Curie temperature of (1-x)[0.88BaTiO₃-0.12Bi(Zn_2/3Nb_1/3)O₃]-xBi_0.5Na_0.5TiO₃ system. Combined with complementary advantages, modified ceramics render a superior energy storage performance (ESP) with a high W_rec of 3.82 J/cm³, efficiency η of 94.4% and prominent temperature tolerance of 25–200 °C at x = 0.3. Moreover, this ceramic exhibit excellent pulse performance, realizing discharge energy storage density W_dis of 2.31 J/cm³ and t_0.9 of 244 ns. Overall, the proposed strategy effectively improved comprehensive properties of BaTiO₃-based ceramics, showing promise in next-generation pulse applications.