Ceramic-Based Dielectric Materials for Energy Storage Capacitor Applications.

Materials offering high energy density are currently desired to meet the increasing demand for energy storage applications, such as pulsed power devices, electric vehicles, high-frequency inverters, and so on. Particularly, ceramic-based dielectric materials have received significant attention for energy storage capacitor applications due to their outstanding properties of high power density, fast charge-discharge capabilities, and excellent temperature stability relative to batteries, electrochemical capacitors, and dielectric polymers. In this paper, we present fundamental concepts for energy storage in dielectrics, key parameters, and influence factors to enhance the energy storage performance, and we also summarize the recent progress of dielectrics, such as bulk ceramics (linear dielectrics, ferroelectrics, relaxor ferroelectrics, and anti-ferroelectrics), ceramic films, and multilayer ceramic capacitors. In addition, various strategies, such as chemical modification, grain refinement/microstructure, defect engineering, phase, local structure, domain evolution, layer thickness, stability, and electrical homogeneity, are focused on the structure-property relationship on the multiscale, which has been thoroughly addressed. Moreover, this review addresses the challenges and opportunities for future dielectric materials in energy storage capacitor applications. Overall, this review provides readers with a deeper understanding of the chemical composition, physical properties, and energy storage performance in this field of energy storage ceramic materials.

Giant Energy Density via Mechanically Tailored Relaxor Ferroelectric Behavior of PZT Thick Film.

Relaxor ferroelectrics (RFEs) are being actively investigated for energy-storage applications due to their large electric-field-induced polarization with slim hysteresis and fast energy charging-discharging capability. Here, a novel nanograin engineering approach based upon high kinetic energy deposition is reported, for mechanically inducing the RFE behavior in a normal ferroelectric Pb(Zr0.52 Ti0.48 )O3 (PZT), which results in simultaneous enhancement in the dielectric breakdown strength (EDBS ) and polarization. Mechanically transformed relaxor thick films with 4 µm thickness exhibit an exceptional EDBS of 540 MV m-1 and reduced hysteresis with large unsaturated polarization (103.6 µC cm-2 ), resulting in a record high energy-storage density of 124.1 J cm-3 and a power density of 64.5 MW cm-3 . This fundamental advancement is correlated with the generalized nanostructure design that comprises nanocrystalline phases embedded within the amorphous matrix. Microstructure-tailored ferroelectric behavior overcomes the limitations imposed by traditional compositional design methods and provides a feasible pathway for realization of high-performance energy-storage materials.

Molten-Salt Processed Potassium Sodium Niobate Single-Crystal Microcuboids with Dislocation-Induced Nanodomain Structures and Relaxor Ferroelectric Behavior.

We herein report a facile molten-salt synthetic strategy to prepare transparent and uniform Li, Ba-doped (K,Na)NbO3 (KNN) single-crystal microcuboids (∼80 µm). By controlling the degree of supersaturation, different growth modes were found and the single-crystal microcuboids were synthesized via island-like oriented attachment of KNN particles onto the growing surface. The distinct relaxor ferroelectric (RFE) properties were achieved in the single-crystal microcuboids, which were different from the normal ferroelectric (FE) properties found in their KNN ceramic counterparts prepared through a solid-state reaction using the same initial precursors. The RFE properties were realized by dislocation-induced nanodomain formation during oriented attachment growth of single-crystal microcuboids, which is different from the current strategies to derive the nanodomains by the local compositional inhomogeneity or the application of an electric field. The dislocations served as nucleation sites for ferroelectric domain walls and block the growth of domains. The KNN single-crystal microcuboids exhibited a higher effective piezoelectric coefficient (∼459 pm/V) compared to that of the bulk KNN ceramic counterpart (∼90 pm/V) and showed the broad diffuse maxima in the temperature dependence dielectric permittivity. The high maximum polarization (69.6 µC/cm2) at a relatively low electric field (30 kV/cm) was beneficial for energy storage applications. Furthermore, the KNN-based transparent, flexible pressure sensor directly monitored the mechanical motion of human activity without any external electric power. This study provides insights and synthetic strategies of single-crystal RFE microcuboids for other different perovskites, in which nanodomain structures are primarily imposed by their chemical composition.

Multiscale surface modified magneto-mechano-triboelectric nanogenerator enabled by eco-friendly NaCl imprinting stamp for self-powered IoT applications.

In this paper, we demonstrated a multiscale micro- and nano-structured magneto-mechano-triboelectric nanogenerator (MMTENG) enabled by a salt particle imprinting process to power an internet of thing (IoT) sensor. The fine salt particles were utilized to form a multiscale structure on a triboelectric polymer film by mechanical pressure via an eco-friendly, low-cost, and simple process, thereby reinforcing the contact triboelectrification and electrostatic induction. The surface modified MMTENG can generate an open-circuit peak-to-peak voltage of 851 V, a short-circuit current of 155 µA, and a maximum peak power of 10.3 mW under an AC magnetic field of 8 Oe. The energy device also presented output stability over 124 million operating cycles. Finally, the electricity of the surface enhanced MMTENG device was directly utilized to power an IoT temperature sensor with integration of an energy harvester, energy conversion circuit, and storage capacitor.

Selective Phase Control of Dopant-Free Potassium Sodium Niobate Perovskites in Solution.

As one of the perovskite families, potassium sodium niobates (K1-xNax)NbO3 (KNN) have been gaining tremendous attention due to their various functional properties which can be largely determined by their crystallographic phase and composition. However, a selective evolution of different phases for KNN with controlled composition can be difficult to achieve, especially in solution chemical synthesis because of its strong tendency to stabilize into orthorhombic phase at conventional synthetic temperature. We herein developed a facile solution approach to control the phase and composition of dopant-free KNN particles selectively through the modification of reaction parameters. A conventional hydrothermal synthesis method yielded orthorhombic KNN particles, while the monoclinic phase, which has never been observed in a bulk counterpart, was kinetically generated by the compositional modification of an intermediate phase under a high-intensity ultrasound irradiation. Cubic KNN particles were stabilized when ethylene glycol was used as a co-solvent together with deionized water through bonding between ethylene glycol molecules and the surface of the KNN. Composite-structured piezoelectric harvesters were fabricated using each phase of KNN particles and the ß-phase poly(vinylidene fluoride-co-trifluoroethylene) polymer. Maximum output power was found for the harvester containing orthorhombic KNN particles. This facile synthetic methodology could pave a new pathway for fabricating numerous phase-controlled materials.

A Comparison Study of Fatigue Behavior of Hard and Soft Piezoelectric Single Crystal Macro-Fiber Composites for Vibration Energy Harvesting.

Designing a piezoelectric energy harvester (PEH) with high power density and high fatigue resistance is essential for the successful replacement of the currently using batteries in structural health monitoring (SHM) systems. Among the various designs, the PEH comprising of a cantilever structure as a passive layer and piezoelectric single crystal-based fiber composites (SFC) as an active layer showed excellent performance due to its high electromechanical properties and dynamic flexibilities that are suitable for low frequency vibrations. In the present study, an effort was made to investigate the reliable performance of hard and soft SFC based PEHs. The base acceleration of both PEHs is held at 7 m/s2 and the frequency of excitation is tuned to their resonant frequency (fr) and then the output power (Prms) is monitored for 107 fatigue cycles. The effect of fatigue cycles on the output voltage, vibration displacement, dielectric, and ferroelectric properties of PEHs was analyzed. It was noticed that fatigue-induced performance degradation is more prominent in soft SFC-based PEH (SS-PEH) than in hard SFC-based PEH (HS-PEH). The HS-PEH showed a slight degradation in the output power due to a shift in fr, however, no degradation in the maximum power was noticed, in fact, dielectric and ferroelectric properties were improved even after 107 vibration cycles. In this context, the present study provides a pathway to consider the fatigue life of piezoelectric material for the designing of PEH to be used at resonant conditions for long-term operation.

Enhancement of Magnetoelectric Conversion Achieved by Optimization of Interfacial Adhesion Layer in Laminate Composites.

We report the effect of epoxy adhesion layers with different mechanical or physical property on a magnetoelectric (ME) composite laminate composed of FeBSi alloy (Metglas)/single-crystal Pb(Mg1/3Nb2/3)O3-Pb(Zr,Ti)O3/Metglas to achieve an improved ME conversion performance. Through theoretical simulation, it was revealed that the Young's modulus and the thickness of interfacial adhesives were major parameters that influence the conversion efficiency in ME composites. In the experimental evaluation, we utilized three epoxy materials with a distinct Young's modulus and adjusted the average thickness of the adhesion layers to optimize the ME conversion. The experimental results show that a thin epoxy layer with a high Young's modulus provided the best performance in the inorganic-based ME conversion process. By tailoring the interfacial adhesion property, the ME laminate generated a high conversion coefficient of 328.8 V/(cm Oe), with a mechanical quality factor of 132.0 at the resonance mode. Moreover, we demonstrated a highly sensitive alternating current magnetic field sensor that had a detection resolution below 10 pT. The optimization of the epoxy layers in the ME laminate composite provided significant enhancement of the ME response in a simple manner.

Boosting the Recoverable Energy Density of Lead-Free Ferroelectric Ceramic Thick Films through Artificially Induced Quasi-Relaxor Behavior.

Dielectric ceramic film capacitors, which store energy in the form of electric polarization, are promising for miniature pulsed power electronic device applications. For a superior energy storage performance of the capacitors, large recoverable energy density, along with high efficiency, high power density, fast charge/discharge rate, and good thermal/fatigue stability, is desired. Herein, we present highly dense lead-free 0.942[Na0.535K0.480NbO3]-0.058LiNbO3 (KNNLN) ferroelectric ceramic thick films (∼5 µm) demonstrating remarkable energy storage performance. The nanocrystalline KNNLN thick film fabricated by aerosol deposition (AD) process and annealed at 600 °C displayed a quasi-relaxor ferroelectric behavior, which is in contrast to the typical ferroelectric nature of the KNNLN ceramic in its bulk form. The AD film exhibited a large recoverable energy density of 23.4 J/cm3, with an efficiency of over 70% under the electric field of 1400 kV/cm. Besides, an ultrahigh power density of 38.8 MW/cm3 together with a fast discharge speed of 0.45 µs, good fatigue endurance (up to 106 cycles), and thermal stability in a wide temperature range of 20-160 °C was also observed. Using the AD process, we could make a highly dense microstructure of the film containing nano-sized grains, which gave rise to the quasi-relaxor ferroelectric characteristics and the remarkable energy storage properties.

Laser Irradiation of Metal Oxide Films and Nanostructures: Applications and Advances.

Recent technological advances in developing a diverse range of lasers have opened new avenues in material processing. Laser processing of materials involves their exposure to rapid and localized energy, which creates conditions of electronic and thermodynamic nonequilibrium. The laser-induced heat can be localized in space and time, enabling excellent control over the manipulation of materials. Metal oxides are of significant interest for applications ranging from microelectronics to medicine. Numerous studies have investigated the synthesis, manipulation, and patterning of metal oxide films and nanostructures. Besides providing a brief overview on the principles governing the laser-material interactions, here, the ongoing efforts in laser irradiation of metal oxide films and nanostructures for a variety of applications are reviewed. Latest advances in laser-assisted processing of metal oxides are summarized.

Enhanced Self-Biased Magnetoelectric Coupling in Laser-Annealed Pb(Zr,Ti)O3 Thick Film Deposited on Ni Foil.

Enhanced and self-biased magnetoelectric (ME) coupling is demonstrated in a laminate heterostructure comprising 4 µm-thick Pb(Zr,Ti)O3 (PZT) film deposited on 50 µm-thick flexible nickel (Ni) foil. A unique fabrication approach, combining room temperature deposition of PZT film by granule spray in vacuum (GSV) process and localized thermal treatment of the film by laser radiation, is utilized. This approach addresses the challenges in integrating ceramic films on metal substrates, which is often limited by the interfacial chemical reactions occurring at high processing temperatures. Laser-induced crystallinity improvement in the PZT thick film led to enhanced dielectric, ferroelectric, and magnetoelectric properties of the PZT/Ni composite. A high self-biased ME response on the order of 3.15 V/cm·Oe was obtained from the laser-annealed PZT/Ni film heterostructure. This value corresponds to a ∼2000% increment from the ME response (0.16 V/cm·Oe) measured from the as-deposited PZT/Ni sample. This result is also one of the highest reported values among similar ME composite systems. The tunability of self-biased ME coupling in PZT/Ni composite has been found to be related to the demagnetization field in Ni, strain mismatch between PZT and Ni, and flexural moment of the laminate structure. The phase-field model provides quantitative insight into these factors and illustrates their contributions toward the observed self-biased ME response. The results present a viable pathway toward designing and integrating ME components for a new generation of miniaturized tunable electronic devices.