Novel BaTiO3-based lead-free ceramic capacitors featuring high energy storage density, high power density, and excellent stability
09 Aug 2018-Journal of Materials Chemistry C (The Royal Society of Chemistry)-Vol. 6, Iss: 31, pp 8528-8537
TL;DR: In this article, a novel BaTiO3-based lead-free composition with an ultrahigh energy storage density (2.41 J cm−3) and a high energy storage efficiency of 91.6% was reported.
Abstract: The development of energy storage devices with a high energy storage density, high power density, and excellent stability has always been a long-cherished goal for many researchers as they tackle issues concerning energy conservation and environmental protection. In this work, we report a novel BaTiO3-based lead-free composition (0.85BaTiO3–0.15Bi(Zn1/2Sn1/2)O3) with an ultrahigh energy storage density (2.41 J cm−3) and a high energy storage efficiency of 91.6%, which is superior to other lead-free systems reported recently. The energy storage properties of 0.85BT–0.15BZS ceramic manifest excellent frequency stability (5–1000 Hz) and fatigue endurance (cycle number: 105). The pulsed charging–discharging process is measured to elucidate the actual operation performance in the 0.85BT–0.15BZS ceramic. Delightfully, the 0.85BT–0.15BZS ceramic also possesses an ultrahigh current density of 551 A cm−2 and a giant power density of 30.3 MW cm−3, and the stored energy is released in sub-microseconds. Moreover, the 0.85BT–0.15BZS ceramic exhibits outstanding temperature stability of its dielectric properties, energy storage properties, and charging–discharging performance over a broad temperature range (20–160 °C) due to the weakly-coupled relaxor behavior. These results not only indicate the superior potential of environment-friendly BaTiO3-based relaxor ferroelectric ceramics for the design of ceramic capacitors of both high energy storage and power applications, but they also show the merit of the weakly-coupled relaxor behavior to improve the thermal stability of energy storage properties.
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TL;DR: In this paper, the authors summarize the principles of dielectric energy-storage applications, and recent developments on different types of Dielectrics, namely linear dielectrics (LDE), paraelectric, ferroelectrics, and antiferro electrics, focusing on perovskite lead-free dielectors.
941 citations
TL;DR: In this paper, the authors proposed a new strategy, namely, grain size engineering, to develop K0.5Na 0.5NbO3 (KNN)-based ceramics with both an extremely high recoverable energy storage density (Wrec) and large mechanical properties.
409 citations
TL;DR: In this article, the fundamental principles of energy storage in dielectric capacitors are introduced and a comprehensive review of the state-of-the-art is presented. But the authors do not consider the use of lead-free materials in high-temperature applications, since their toxicity raises concern over their use in consumer applications.
Abstract: 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.
396 citations
TL;DR: In this paper, the authors presented an innovative strategy to improve the energy storage properties of NaNbO3 lead-free ceramics by the addition of Bi2O3.
Abstract: This study presents an innovative strategy to improve the energy storage properties of NaNbO3 lead-free ceramics by the addition of Bi2O3. The introduction of Bi2O3 can effectively increase the breakdown strength and decrease the remnant polarization of NaNbO3 ceramics. Meanwhile, hybridization between the O2− 2p and Bi3+ 6p orbitals can enhance the polarization. The novel NaNbO3-based (Na0.7Bi0.1NbO3) ceramics demonstrate ultrahigh energy storage efficiency of 85.4% and remarkably high energy storage density (4.03 J cm−3) at 250 kV cm−1 simultaneously, which are superior to the results of almost all recently reported lead-free alternatives. The outstanding stability of energy storage characteristics in terms of frequency (1–1000 Hz), temperature (20–120 °C) and fatigue (cycle number: 105) is also observed in Na0.7Bi0.1NbO3 ceramics. Furthermore, additional pulsed charge–discharge measurements for Na0.7Bi0.1NbO3 ceramics are also carried out to evaluate actual operation performance. The Na0.7Bi0.1NbO3 ceramics exhibit extremely high power density (62.5 MW cm−3) and current density (1250 A cm−2) and release all stored energy rapidly (∼155 ns) under various electric fields and temperatures. These properties qualify these environment-friendly Na0.7Bi0.1NbO3 ceramics as innovative and most promising alternatives for energy storage applications, especially for high power and pulsed power system applications.
322 citations
References
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TL;DR: The effective ionic radii of Shannon & Prewitt [Acta Cryst. (1969), B25, 925-945] are revised to include more unusual oxidation states and coordinations as mentioned in this paper.
Abstract: The effective ionic radii of Shannon & Prewitt [Acta Cryst. (1969), B25, 925-945] are revised to include more unusual oxidation states and coordinations. Revisions are based on new structural data, empirical bond strength-bond length relationships, and plots of (1) radii vs volume, (2) radii vs coordination number, and (3) radii vs oxidation state. Factors which affect radii additivity are polyhedral distortion, partial occupancy of cation sites, covalence, and metallic character. Mean Nb5+-O and Mo6+-O octahedral distances are linearly dependent on distortion. A decrease in cation occupancy increases mean Li+-O, Na+-O, and Ag+-O distances in a predictable manner. Covalence strongly shortens Fe2+-X, Co2+-X, Ni2+-X, Mn2+-X, Cu+-X, Ag+-X, and M-H- bonds as the electronegativity of X or M decreases. Smaller effects are seen for Zn2+-X, Cd2+-X, In2+-X, pb2+-X, and TI+-X. Bonds with delocalized electrons and therefore metallic character, e.g. Sm-S, V-S, and Re-O, are significantly shorter than similar bonds with localized electrons.
51,997 citations
TL;DR: In this paper, the authors report results of electronic-structure calculations on two classic examples of ferroelectric perovskites, BaTiO3 and PbTiO2, and demonstrate that hybridization between the titanium 3d states and the oxygen 2p states is essential for ferroelectivity.
Abstract: FERROELECTRIC materials are characterized by a switchable macroscopic polarization. Most technologically important ferroelectrics are oxides with a perovskite structure. The origin of their ferroelectric behaviour is unclear, however, and there is incomplete understanding of why similar, but chemically different, perovskites should display very different ferroelectric behaviour. The great sensitivity of ferroelectrics to chemistry, defects, electrical boundary conditions and pressure arises from a delicate balance between long-range Coulomb forces (which favour the ferroelectric state) and short-range repulsions (which favour the nonpolar cubic structure). To model the transition accurately, total-energy techniques are required which incorporate the effects of charge distortion and covalency. Here I report results of electronic-structure calculations on two classic examples of ferroelectric perovskites, BaTiO3 and PbTiO3, and demonstrate that hybridization between the titanium 3d states and the oxygen 2p states is essential for ferroelectricity. The different ferroelectric phase behaviour of the two materials is also clear: in PbTiO3, the lead and oxygen states hybridize, leading to a large strain that stabilizes the tetragonal phase, whereas in BaTiO3 the interaction between barium and oxygen is completely ionic, favouring a rhombohedral structure.
2,417 citations
TL;DR: It is demonstrated that a very high energy density with fast discharge speed and low loss can be obtained in defect-modified poly(vinylidene fluoride) polymers by combining nonpolar and polar molecular structural changes of the polymer with the proper dielectric constants.
Abstract: Dielectric polymers with high dipole density have the potential to achieve very high energy density, which is required in many modern electronics and electric systems. We demonstrate that a very high energy density with fast discharge speed and low loss can be obtained in defect-modified poly(vinylidene fluoride) polymers. This is achieved by combining nonpolar and polar molecular structural changes of the polymer with the proper dielectric constants, to avoid the electric displacement saturation at electric fields well below the breakdown field. The results indicate that a very high dielectric constant may not be desirable to reach a very high energy density.
2,008 citations
TL;DR: In this article, the dielectric relaxation of a solid solution of lead titanate in lead magnesium niobate is found to be similar to the magnetic relaxation in spin-glass systems.
Abstract: The dielectric relaxation of a solid solution of 10‐mol % lead titanate in lead magnesium niobate is found to be similar to the magnetic relaxation in spin‐glass systems.1–3 Based on this analogy, it is proposed that the relaxor ferroelectric is a polar‐glassy system which has thermally activated polarization fluctuations above a static freezing temperature. An activation energy and freezing temperature of 0.0407 eV and 291.5 K, respectively, were found by analyzing the frequency dependence of the temperature of the dielectric maximum using the Vogel–Fulcher relationship.4,5 It has also been shown that a macroscopic polarization is sustained on heating up to this freezing temperature. A coupling between nanometer scale clusters is believed to control the kinetics of the fluctuations and the development of a frustration as the system freezes into states of local equilibrium. The possibility of an orientational freezing associated with the ferroelastic nature of the nanosized polar regions in the rhombohedr...
1,148 citations
TL;DR: This review first outlines the crucial issues in the nanodielectric field and then focuses on recent remarkable research developments in the fabrication of FNDMs with special constitutents, molecular structures, and microstructures.
Abstract: Study of flexible nanodielectric materials (FNDMs) with high permittivity is one of the most active academic research areas in advanced functional materials. FNDMs with excellent dielectric properties are demonstrated to show great promise as energy-storage dielectric layers in high-performance capacitors. These materials, in common, consist of nanoscale particles dispersed into a flexible polymer matrix so that both the physical/chemical characteristics of the nanoparticles and the interaction between the nanoparticles and the polymers have crucial effects on the microstructures and final properties. This review first outlines the crucial issues in the nanodielectric field and then focuses on recent remarkable research developments in the fabrication of FNDMs with special constitutents, molecular structures, and microstructures. Possible reasons for several persistent issues are analyzed and the general strategies to realize FNDMs with excellent integral properties are summarized. The review further highlights some exciting examples of these FNDMs for power-energy-storage applications.
1,131 citations