Current development, optimisation strategies and future perspectives for lead-free dielectric ceramics in high field and high energy density capacitors.

To meet the United Nations' sustainable development goal of affordable and clean energy, there has been a growing need for low-cost, green, and safe energy storage technologies. High-field and energy-density capacitors have gained substantial attention from academics and industry, particularly for power electronics, where they will play a key role in optimising the performance of management systems in electric vehicles. The key figure of merit, energy density (Wrec), for high-field applications has dramatically increased year-on-year from 2020 to 2024, as evidenced by over 250 papers, demonstrating ever larger Wrec values. This review briefly introduces the background and principles of high energy density ceramics, but its focus is to provide constructive and comprehensive insight into the evaluation of Wrec, Emax, ΔP, and η, and more importantly, the normalised metrics, Wrec/Emax and Wrec/ΔP in lead-free dielectric ceramics. We also present several optimisation strategies for materials modification and process innovation that have been recently proposed before providing perspectives for the further development of high-field and high-energy density capacitors.

Multiple Local Symmetries Result in a Common Average Polar Axis in High-Strain BiFeO_{3}-Based Ceramics.

For the first time, the origin of large electrostrain in pseudocubic BiFeO_{3}-based ceramics is verified with direct structural evidence backed by appropriate simulations. We employ advanced structural and microstructural characterizations of BiFeO_{3}-based ceramics that exhibit large electrostrain (>0.4%) to reveal the existence of multiple, nanoscale local symmetries, dominantly tetragonal or orthorhombic, which have a common, averaged direction of polarization over larger, meso- or microscale regions. Phase-field simulations confirm the existence of local nanoscale symmetries, thereby providing a new vision for designing high-performance lead-free ceramics for high-strain actuators.

Electroceramics for High-Energy Density Capacitors: Current Status and Future Perspectives.

Materials exhibiting high energy/power density are currently needed to meet the growing demand of portable electronics, electric vehicles and large-scale energy storage devices. The highest energy densities are achieved for fuel cells, batteries, and supercapacitors, but conventional dielectric capacitors are receiving increased attention for pulsed power applications due to their high power density and their fast charge-discharge speed. The key to high energy density in dielectric capacitors is a large maximum but small remanent (zero in the case of linear dielectrics) polarization and a high electric breakdown strength. Polymer dielectric capacitors offer high power/energy density for applications at room temperature, but above 100 °C they are unreliable and suffer from dielectric breakdown. For high-temperature applications, therefore, dielectric ceramics are the only feasible alternative. Lead-based ceramics such as La-doped lead zirconate titanate exhibit good energy storage properties, but their toxicity raises concern over their use in consumer applications, where capacitors are exclusively lead free. Lead-free compositions with superior power density are thus required. In this paper, we introduce the fundamental principles of energy storage in dielectrics. We discuss key factors to improve energy storage properties such as the control of local structure, phase assemblage, dielectric layer thickness, microstructure, conductivity, and electrical homogeneity through the choice of base systems, dopants, and alloying additions, followed by a comprehensive review of the state-of-the-art. Finally, we comment on the future requirements for new materials in high power/energy density capacitor applications.

Synthesis of Barium Titanate Using Deep Eutectic Solvents.

Novel synthetic routes to prepare functional oxides at lower temperatures are an increasingly important area of research. Many of these synthetic routes, however, use water as the solvent and rely on dissolution of the precursors, precluding their use with, for example, titanates. Here we present a low-cost solvent system as a means to rapidly create phase-pure ferroelectric barium titanate using a choline chloride-malonic acid deep eutectic solvent. This solvent is compatible with alkoxide precursors and allows for the rapid synthesis of nanoscale barium titanate powders at 950 °C. The phase and morphology were determined, along with investigation of the synthetic pathway, with the reaction proceeding via BaCl2 and TiO2 intermediates. The powders were also used to create sintered ceramics, which exhibit a permittivity maximum corresponding to a tetragonal-cubic transition at 112 °C, as opposed to the more conventional temperature of ∼120 °C. The lower-than-expected value for the ferro- to para-electric phase transition is likely due to undetectable levels of contaminants.

Growth of BiFeO3 thin films by chemical solution deposition: the role of electrodes.

BiFeO3 (BFO) thin films were grown by chemical solution deposition on a range of electrodes to determine their role in controlling the phase formation and microstructure of the films. The crystallization on oxide electrodes followed the sequence: amorphous → Bi2O2(CO3) → perovskite, while those on Pt crystallized directly from the amorphous phase. IrO2 electrodes promoted perovskite phase formation at the lowest temperature and LaNiO3 additionally induced local epitaxial growth. All compositions exhibited fully coherent Fe-rich precipitates within the grain interior of the perovskite matrix, whereas the incoherent Bi2Fe4O9 second phase was also observed at the grain boundaries of BFO grown on Pt electrodes. The latter could be observed by X-ray diffraction as well as transmission electron microscopy (TEM) but coherent precipitates were only observed by TEM, principally evidenced by their Z contrast in annular dark field images. These data have pronounced consequences for the extended use of BFO films under an applied field for actuator, sensor and memory applications.

A family of oxide ion conductors based on the ferroelectric perovskite Na0.5Bi0.5TiO3.

Oxide ion conductors find important technical applications in electrochemical devices such as solid-oxide fuel cells (SOFCs), oxygen separation membranes and sensors. Na0.5Bi0.5TiO3 (NBT) is a well-known lead-free piezoelectric material; however, it is often reported to possess high leakage conductivity that is problematic for its piezo- and ferroelectric applications. Here we report this high leakage to be oxide ion conduction due to Bi-deficiency and oxygen vacancies induced during materials processing. Mg-doping on the Ti-site increases the ionic conductivity to ~0.01 S cm(-1) at 600 °C, improves the electrolyte stability in reducing atmospheres and lowers the sintering temperature. This study not only demonstrates how to adjust the nominal NBT composition for dielectric-based applications, but also, more importantly, gives NBT-based materials an unexpected role as a completely new family of oxide ion conductors with potential applications in intermediate-temperature SOFCs and opens up a new direction to design oxide ion conductors in perovskite oxides.

Unveiling the Role of CNTs in the Phase Formation of One-Dimensional Ferroelectrics.

Carbon nanotubes (CNTs) have the potential to act as templates or bottom electrodes for three-dimensional (3D) capacitor arrays, which utilize one-dimensional (1D) ferroelectric nanostructures to increase the memory size and density. However, growing a ferroelectric on the surface of CNTs is nontrivial. Here, we demonstrate that multiwalled (MW) CNTs decrease the time and temperature for the formation of lead zirconium titanate Pb(Zr1-xTix)O3 (PZT) by ∼100 °C commensurate with a decrease in activation energy from 68 ± 15 to 27 ± 2 kJ/mol. As a consequence, monophasic PZT was obtained at 575 °C for MWCNTs/PZT, but for pure PZT, traces of pyrochlore were still present at 650 °C, where the PZT phase formed due to homogeneous nucleation. The piezoelectric nature of MWCNTs/PZT synthesized at 500 °C for 1 h was proven. Although further work is required to prove the concept of 3D capacitor arrays, our result suggests that it is feasible to utilize MWCNTs as templates/electrodes for the formation of 1D PZT nanoferroelectrics.

Aqueous Cold Sintering of Li-Based Compounds.

Aqueous cold sintering of two lithium-based compounds, the electrolyte Li6.25La3Zr2Al0.25O12 (LLZAO) and cathode material LiCoO2 (LCO), is reported. For LLZAO, a relative density of ∼87% was achieved, whereas LCO was sintered to ∼95% with 20 wt % LLZAO as a flux/binder. As-cold sintered LLZAO exhibited a low total conductivity (10-8 S/cm) attributed to an insulating grain boundary blocking layer of Li2CO3. The blocking layer was reduced with a post-annealing process or, more effectively, by replacing deionized water with 5 M LiCl during cold sintering to achieve a total conductivity of ∼3 × 10-5 S/cm (similar to the bulk conductivity). For LCO-LLZAO composites, scanning electron microscopy and X-ray computer tomography indicated a continuous LCO matrix with the LLZAO phase evenly distributed but isolated throughout the ceramics. [001] texturing during cold sintering resulted in an order of magnitude difference in electronic conductivity between directions perpendicular and parallel to the c-axis at room temperature. The electronic conductivity (∼10-2 S/cm) of cold sintered LCO-LLZAO ceramics at room temperature was comparable to that of single crystals and higher than those synthesized via either conventional sintering or hot pressing.

Dynamic tilting in perovskites.

A new computational analysis of tilt behaviour in perovskites is presented. This includes the development of a computational program - PALAMEDES - to extract tilt angles and the tilt phase from molecular dynamics simulations. The results are used to generate simulated selected-area electron and neutron diffraction patterns which are compared with experimental patterns for CaTiO3. The simulations not only reproduced all symmetrically allowed superlattice reflections associated with tilt but also showed local correlations that give rise to symmetrically forbidden reflections and the kinematic origin of diffuse scattering.

Novel Method to Achieve Temperature-Stable Microwave Dielectric Ceramics: A Case in the Fergusonite-Structured NdNbO4 System.

Microwave dielectric ceramics with permittivity (εr) ∼ 20 play an important role in massive multiple-input multiple-output (MIMO) technology in 5G. Although fergusonite-structured materials with low dielectric loss are good candidates for 5G application, tuning the temperature coefficient of resonant frequency (TCF) remains a problem. In the present work, smaller V5+ ions (rV = 0.355 Å, with coordination number (CN) = 4) were substituted for Nb5+ (rNb = 0.48 Å with CN = 4) in the Nd(Nb1-xVx)O4 ceramics, which, according to in situ X-ray diffraction data, lowered the fergusonite-to-scheelite phase transition (TF-S) to 400 °C for x = 0.2. The thermal expansion coefficient (αL) of the high-temperature scheelite phase was +11 ppm/°C, whereas for the low-temperature fergusonite phase, it was + 14 < αL < + 15 ppm/°C. The abrupt change in αL, the associated negative temperature coefficient of permittivity (τε), and the minimum value of εr at TF-S resulted in a near-zero TCF ∼ (+7.8 ppm/°C) for Nd(Nb0.8V0.2)O4 (εr ∼ 18.6 and Qf ∼ 70,100 GHz). A method to design near-zero TCF compositions based on modulation of τε and αL at TF-S is thus demonstrated that may also be extended to other fergusonite systems.

Determination of relative in vivo osteoconductivity of modified potassium fluorrichterite glass-ceramics compared with 45S5 bioglass.

Potassium fluorrichterite (KNaCaMg(5)Si(8)O(22)F(2)) glass-ceramics were modified by either increasing the concentration of calcium (GC5) or by the addition of P(2)O(5) (GP2). Rods (2 × 4 mm) of stoichiometric fluorrichterite (GST), modified compositions (GC5 and GP2) and 45S5 bioglass, which was used as the reference material, were prepared using a conventional lost-wax technique. Osteoconductivity was investigated by implantation into healing defects in the midshaft of rabbit femora. Specimens were harvested at 4 and 12 weeks following implantation and tissue response was investigated using computed microtomography (µCT) and histological analyses. The results showed greatest bone to implant contact in the 45S5 bioglass reference material at 4 and 12 weeks following implantation, however, GST, GC5 and GP2 all showed direct bone tissue contact with evidence of new bone formation and cell proliferation along the implant surface into the medullary space. There was no evidence of bone necrosis or fibrous tissue encapsulation around the test specimens. Of the modified potassium fluorrichterite compositions, GP2 showed the greatest promise as a bone substitute material due to its osteoconductive potential and superior mechanical properties.

Design and Fabrication of a C-Band Dielectric Resonator Antenna with Novel Temperature-Stable Ce(Nb1-xVx)NbO4 (x = 0-0.4) Microwave Ceramics.

Vanadium(V)-substituted cerium niobate [Ce(Nb1-xVx)O4, CNVx] ceramics were prepared to explore their structure-microwave (MW) property relations and application in C-band dielectric resonator antennas (DRAs). X-ray diffraction and Raman spectroscopy revealed that CNVx (0.0 ≤ x ≤ 0.4) ceramics exhibited a ferroelastic phase transition at a critical content of V (xc = 0.3) from a monoclinic fergusonite structure to a tetragonal scheelite structure (TF-S), which decreased in temperature as a function of x according to thermal expansion analysis. Optimum microwave dielectric performance was obtained for CNV0.3 with permittivity (εr) of ∼16.81, microwave quality factor (Qf) of ∼41 300 GHz (at ∼8.7 GHz), and temperature coefficient of the resonant frequency (TCF) of ∼ -3.5 ppm/°C. εr is dominated by Ce-O phonon absorption in the microwave band; Qf is mainly determined by the porosity, grain size, and proximity of TF-S; and TCF is controlled by the structural distortions associated with TF-S. Terahertz (THz) (0.20-2.00 THz, εr ∼ 12.52 ± 0.70, and tan δ ∼ 0.39 ± 0.17) and infrared measurements are consistent, demonstrating that CNVx (0.0 ≤ x ≤ 0.4) ceramics are effective in the sub-millimeter as well as MW regime. A cylindrical DRA prototype antenna fabricated from CNV0.3 resonated at 7.02 GHz (|S11| = -28.8 dB), matching simulations, with >90% radiation efficiency and 3.34-5.93 dB gain.

In vitro biocompatibility of modified potassium fluorrichterite and potassium fluorrichterite-fluorapatite glass-ceramics.

Potassium fluorrichterite (KNaCaMg(5)Si(8)O(22)F(2)) glass-ceramics were modified by either increasing the concentration of calcium in the glass (GC5), or by the addition of P(2)O(5) to produce potassium fluorrichterite-fluorapatite (GP2). The solubility of the stoichiometric composition (GST), GC5 and GP2 were measured using the standard test described in ISO 6872:1995 (Dental Ceramics). Ion release profiles were determined for Si, Ca, Mg, Na, K and P using inductively coupled plasma mass spectrometry and fluoride ion (F(-)) concentration was measured using an ion-selective electrode. The cytotoxicity of all compositions was assessed using cultured rat osteosarcoma cells (ROS, 17/2.8). Cell response was qualitatively assessed using scanning electron microscopy (SEM) and quantitatively using the Alamar blue assay. GST was the least soluble and also released the lowest concentration of ions following immersion in water. Of the modified compositions, GC5 demonstrated intermediate solubility but the greatest ion release while GP2 exhibited the highest solubility. This was most likely due to GC5 having the greatest proportion of residual glass following crystallisation. The mass loss exhibited by GP2 may have been due in part to the partial disintegration of the surface of specimens during solubility testing. SEM demonstrated that all compositions supported the growth of healthy ROS cells on their surfaces, and this data was further supported by the quantitative Alamar blue assay.

Prediction of osteoconductive activity of modified potassium fluorrichterite glass-ceramics by immersion in simulated body fluid.

Potassium fluorrichterite (KNaCaMg(5)Si(8)O(22)F(2)) glass-ceramics were modified by either increasing the concentration of calcium (GC5) or by the addition of P(2)O(5) (GP2). The stoichiometric composition (GST), GC5 and GP2 were soaked in simulated body fluid (SBF) along with 45S5-type bioglass as a control. After immersion, surface analyses were performed using thin-film X-ray diffraction (TF-XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS) and Fourier-transform infrared (reflection) spectroscopy (FT-IR). All compositions showed the formation of a calcium phosphate rich surface layer in SBF; GST, GP2 and the bioglass control within 7 days of immersion and GC5 after 14 days. It was concluded that all compositions were likely to be osteoconductive in vivo, with GP2 providing the best performance in terms of the combination of rapid formation of the surface layer and superior mechanical properties. This glass-ceramic system has potential as a load bearing bioceramic for fabrication of medical devices intended for skeletal tissue repair.

Towards revealing key factors in mechanical instability of bioabsorbable Zn-based alloys for intended vascular stenting.

Zn-based alloys are recognized as promising bioabsorbable materials for cardiovascular stents, due to their biocompatibility and favorable degradability as compared to Mg. However, both low strength and intrinsic mechanical instability arising from a strong strain rate sensitivity and strain softening behavior make development of Zn alloys challenging for stent applications. In this study, we developed binary Zn-4.0Ag and ternary Zn-4.0Ag-xMn (where x = 0.2-0.6wt%) alloys. An experimental methodology was designed by cold working followed by a thermal treatment on extruded alloys, through which the effects of the grain size and precipitates could be thoroughly investigated. Microstructural observations revealed a significant grain refinement during wire drawing, leading to an ultrafine-grained (UFG) structure with a size of 700 nm and 200 nm for the Zn-4.0Ag and Zn-4.0Ag-0.6Mn, respectively. Mn showed a powerful grain refining effect, as it promoted the dynamic recrystallization. Furthermore, cold working resulted in dynamic precipitation of AgZn3 particles, distributing throughout the Zn matrix. Such precipitates triggered mechanical degradation through an activation of Zn/AgZn3 boundary sliding, reducing the tensile strength by 74% and 57% for Zn-4.0Ag and Zn-4.0Ag-0.6Mn, respectively. The observed precipitation softening caused a strong strain rate sensitivity in cold drawn alloys. Short-time annealing significantly mitigated the mechanical instability by reducing the AgZn3 fraction. The ternary alloy wire showed superior microstructural stability relative to its Mn-free counterpart due to the pinning effect of Mn-rich particles on the grain boundaries. Eventually, a shift of the corrosion regime from localized to more uniform was observed after the heat treatment, mainly due to the dissolution of AgZn3 precipitates. STATEMENT OF SIGNIFICANCE: Owing to its promising biodegradability, zinc has been recognized as a potential biodegradable material for stenting applications. However, Zn's poor strength alongside intrinsic mechanical instability have propelled researchers to search for Zn alloys with improved mechanical properties. Although extensive researches have been conducted to satisfy the mentioned concerns, no Zn-based alloys with stabilized mechanical properties have yet been reported. In this work, the mechanical properties and stability of the Zn-Ag-based alloys were systematically evaluated as a function of microstructural features. We found that the microstructure design in Zn alloys can be used to find an effective strategy to not only improve the strength and suppress the mechanical instability but also to minimize any damage by augmenting the corrosion uniformity.

Novel BaTiO3-Based, Ag/Pd-Compatible Lead-Free Relaxors with Superior Energy Storage Performance.

Ceramic dielectrics are reported with superior energy storage performance for applications, such as power electronics in electrical vehicles. A recoverable energy density (Wrec) of ∼4.55 J cm-3 with η ∼ 90% is achieved in lead-free relaxor BaTiO3-0.06Bi2/3(Mg1/3Nb2/3)O3 ceramics at ∼520 kV cm-1. These ceramics may be co-fired with Ag/Pd, which constitutes a major step forward toward their potential use in the fabrication of commercial multilayer ceramic capacitors. Compared to stoichiometric Bi(Mg2/3Nb1/3)O3-doped BaTiO3 (BT), A-site deficient Bi2/3(Mg1/3Nb2/3)O3 reduces the electrical heterogeneity of BT. Bulk conductivity differs from the grain boundary only by 1 order of magnitude which, coupled with a smaller volume fraction of conducting cores due to enhanced diffusion of the dopant via A-site vacancies in the A-site sublattice, results in higher breakdown strength under an electric field. This strategy can be employed to develop new dielectrics with improved energy storage performance.

Temperature Stable Cold Sintered (Bi0.95Li0.05)(V0.9Mo0.1)O4-Na2Mo2O7 Microwave Dielectric Composites.

Dense (Bi0.95Li0.05)(V0.9Mo0.1)O4-Na2Mo2O7 (100-x) wt.% (Bi0.95Li0.05)(V0.9Mo0.1)O4 (BLVMO)-x wt.% Na2Mo2O7 (NMO) composite ceramics were successfully fabricated through cold sintering at 150 °C under at 200 MPa for 30 min. X-ray diffraction, back-scattered scanning electron microscopy, and Raman spectroscopy not only corroborated the coexistence of BLVMO and NMO phases in all samples, but also the absence of parasitic phases and interdiffusion. With increasing NMO concentration, the relative pemittivity (εr) and the Temperature Coefficient of resonant Frequency (TCF) decreased, whereas the Microwave Quality Factor (Qf) increased. Near-zero TCF was measured for BLVMO-20wt.%NMO composites which exhibited εr ~ 40 and Qf ~ 4000 GHz. Finally, a dielectric Graded Radial INdex (GRIN) lens was simulated using the range of εr in the BLVMO-NMO system, which predicted a 70% aperture efficiency at 26 GHz, ideal for 5G applications.

Nanoscale Mapping of Bromide Segregation on the Cross Sections of Complex Hybrid Perovskite Photovoltaic Films Using Secondary Electron Hyperspectral Imaging in a Scanning Electron Microscope.

Mixed halide (I/Br) complex organic/inorganic hybrid perovskite materials have attracted much attention recently because of their excellent photovoltaic properties. Although it has been proposed that their stability is linked to the chemical inhomogeneity of I/Br, no direct proof has been offered to date. Here, we report a new method, secondary electron hyperspectral imaging (SEHI), which allows direct imaging of the local variation in Br concentration in mixed halide (I/Br) organic/inorganic hybrid perovskites on a nanometric scale. We confirm the presence of a nonuniform Br distribution with variation in concentration within the grain interiors and boundaries and demonstrate how SEHI in conjunction with low-voltage scanning electron microscopy can enhance the understanding of the fundamental physics and materials science of organic/inorganic hybrid photovoltaics, illustrating its potential for research and development in "real-world" applications.

Crystal Structure, Infrared Spectra, and Microwave Dielectric Properties of Temperature-Stable Zircon-Type (Y,Bi)VO4 Solid-Solution Ceramics.

A series of (Bi1-x Y x )VO4 (0.4 ≤ x ≤ 1.0) ceramics were synthesized using the traditional solid-state reaction method. In the composition range of 0.4 ≤ x ≤ 1.0, a zircon-type solid solution was formed between 900 and 1550 °C. Combined with our previous work (scheelite monoclinic and zircon-type phases coexist in the range of x < 0.40), a pseudobinary phase diagram of BiVO4-YVO4 is presented. As x decreased from 1.0 to 0.40, the microwave permittivity (εr) of (Bi1-x Y x )VO4 ceramics increased linearly from 11.03 to 30.9, coincident with an increase in the temperature coefficient of resonant frequency (TCF) from -61.3 to +103 ppm/°C. Excellent microwave dielectric properties were obtained for (Bi0.3Y0.7)VO4 sintered at 1025 °C and (Bi0.2Y0.8)VO4 sintered at 1075 °C with εr ∼ 19.35, microwave quality factor (Qf) ∼ 25 760 GHz, and TCF ∼ +17.8 ppm/°C and εr ∼ 16.3, Qf ∼ 31 100 GHz, and TCF ∼ -11.9 ppm/°C, respectively. Raman spectra, Shannon's additive rule, a classical oscillator model, and far-infrared spectra were employed to study the structure-property relations in detail. All evidence supported the premise that Bi-based vibrations dominate the dielectric permittivity in the microwave region.