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.

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.

Lead-free BNT composite film for high-frequency broadband ultrasonic transducer applications.

A lead-free Bi0.5Na0.5TiO3 (BNT) piezoelectric composite thick film with a thickness of ~11 µm has been fabricated using a modified sol-gel method. Dielectric constant, remnant polarization, and coercive field of the BNT composite film were found to be 1018, 22.6 µC/cm2, and 76.1 kV/cm, respectively. The film was used to fabricate a high-frequency needle transducer and the performance of the transducer was measured. The transducer without a matching layer exhibits a center frequency of 98 MHz and a -6-dB bandwidth of 86%. A wire phantom image acquired using the transducer shows an axial resolution of 15 ¿m and lateral resolution of 68 µm, respectively. Results from this study suggest that the BNT composite film is a promising lead-free piezoelectric material for high-frequency broadband ultrasonic transducer applications.

Structure and electrical properties of Na0.5Bi0.5TiO3 ferroelectric thick films derived from a polymer modified sol-gel method.

Lead-free NaBi(0.5)TiO(3) (NBT) ferroelectric thick films were prepared by a poly(vinylpyrrolidone) (PVP) modified sol-gel method. The NBT thick films annealed from 500°C to 750°C exhibit a perovskite structure. The relationship between annealing temperature, thickness, and electrical properties of the thick films has been investigated. The dielectric constants and remnant polarizations of the thick films increase with annealing temperature. The electrical properties of the NBT films show strong thickness dependence. As thickness increases from 1.0 to 4.8 µm, the dielectric constant of the NBT films increases from 620 to 848, whereas the dielectric loss is nearly independent of the thickness. The remnant polarization of the NBT thick films also increases with increasing thickness. The leakage current density first decreases and then increases with film thickness.

Synthesis of a Au/silica/polymer trilayer composite and the corresponding hollow polymer microsphere with a movable Au core.

Gold/silica/poly(N,N'-methylenebisacrylamide) (Au/SiO2/polyMBAAm) trilayer composite materials were prepared by distillation precipitation polymerization of N,N'-methylenebisacrylamide (MBAAm) in the presence of Au/SiO2 particles as seeds, in which the seeds were prepared by a combination of gold-complexing and silane coupling agent with a further modified Stöber method. The polymerization of MBAAm was performed in neat acetonitrile with 2,2'-azobisisobutyronitrile as an initiator to encapsulate the Au/SiO2 seeds driven by the hydrogen-bonding interaction between the hydroxyl group on the surface of the seeds and the amide unit of polyMBAAm without modification of the Au/SiO2 surface in the absence of any stabilizer or surfactant. Hollow polyMBAAm microspheres with movable Au cores were further developed by the selective removal of the middle silica layer with hydrofluoric acid. The resultant trilayer Au/SiO2/polyMBAAm composite and hollow polyMBAAm microspheres with movable Au cores were characterized by transmission electron microscopy. The diffusion of chemicals across the polyMBAAm shell was investigated by a catalytic reduction of 4-nitrophenol to 4-aminophenol in the presence of sodium borohydride as a reductant.