Superior energy storage properties and excellent stability of novel NaNbO3-based lead-free ceramics with A-site vacancy obtained via a Bi2O3 substitution strategy
25 Sep 2018-Journal of Materials Chemistry (The Royal Society of Chemistry)-Vol. 6, Iss: 37, pp 17896-17904
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.
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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
Abstract: A novel lead-free polar dielectric ceramic with linear-like polarization responses was found in (1 − x)(Bi0.5Na0.5)TiO3–xNaNbO3 ((1 − x)BNT–xNN) solid solutions, exhibiting giant energy storage density/efficiency and super stability against temperature and frequency. High-resolution transmission electron microscopy, Raman scattering and Rietveld refinements of X-ray diffraction data suggest that these property characteristics can be derived from temperature and electric field insensitive large permittivity as a result of relaxor antiferroelectricity (AFE) with polar nanoregions. Additionally, this feature intrinsically requires a high driving field for AFE to ferroelectric (FE) phase transitions due to large random fields. Measurements of temperature-dependent permittivity and polarization versus electric field hysteresis loops indicate that the high-temperature AFE P4bm phase in BNT was gradually stabilized close to room temperature, accompanying a phase transition from relaxor rhombohedral FEs to relaxor tetragonal AFEs approximately at x = 0.15–0.2. A record high of recoverable energy-storage density W ∼ 7.02 J cm−3 as well as a high efficiency η ∼ 85% was simultaneously achieved in the x = 0.22 bulk ceramic, which challenges the existing fact that W and η must be seriously compromised. Furthermore, desirable W (>3.5 J cm−3) and η (>88%) with a variation of less than 10% can be accordingly obtained in the temperature range of 25–250 °C and frequency range of 0.1–100 Hz. These excellent energy-storage properties would make BNT-based lead-free AFE ceramic systems a potential candidate for application in pulsed power systems.
359 citations
TL;DR: In this article, a new environment-friendly 0.76NaNbO3-0.24(Bi0.5Na 0.5)TiO3 relaxor antiferroelectric (AFE) bulk ceramic is studied, where local orthorhombic Pnma symmetry (R phase) and nanodomains are observed based on high-resolution transmission electron microscopy, selected area electron diffraction, and in/ex situ synchrotron X-ray diffraction.
Abstract: Dielectric energy-storage capacitors have received increasing attention in recent years due to the advantages of high voltage, high power density, and fast charge/discharge rates. Here, a new environment-friendly 0.76NaNbO3–0.24(Bi0.5Na0.5)TiO3 relaxor antiferroelectric (AFE) bulk ceramic is studied, where local orthorhombic Pnma symmetry (R phase) and nanodomains are observed based on high-resolution transmission electron microscopy, selected area electron diffraction, and in/ex situ synchrotron X-ray diffraction. The orthorhombic AFE R phase and relaxor characteristics synergistically contribute to the record-high energy-storage density Wrec of ≈12.2 J cm−3 and acceptable energy efficiency η ≈ 69% at 68 kV mm−1, showing great advantages over currently reported bulk dielectric ceramics. In comparison with normal AFEs, the existence of large random fields in the relaxor AFE matrix and intrinsically high breakdown strength of NaNbO3-based compositions are thought to be responsible for the observed energy-storage performances. Together with the good thermal stability of Wrec (>7.4 J cm−3) and η (>73%) values at 45 kV mm−1 up to temperature of 200 °C, it is demonstrated that NaNbO3-based relaxor AFE ceramics will be potential lead-free dielectric materials for next-generation pulsed power capacitor applications.
354 citations
References
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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: 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
TL;DR: It is revealed that the incorporation of Ta to the Nb site can enhance the antiferroelectricity because of the reduced polarizability of B-site cations, which is confirmed by the polarization hysteresis, dielectric tunability, and selected-area electron diffraction measurements.
Abstract: Antiferroelectric materials that display double ferroelectric hysteresis loops are receiving increasing attention for their superior energy storage density compared to their ferroelectric counterparts. Despite the good properties obtained in antiferroelectric La-doped Pb(Zr,Ti)O3 -based ceramics, lead-free alternatives are highly desired due to the environmental concerns, and AgNbO3 has been highlighted as a ferrielectric/antiferroelectric perovskite for energy storage applications. Enhanced energy storage performance, with recoverable energy density of 4.2 J cm-3 and high thermal stability of the energy storage density (with minimal variation of ≤±5%) over 20-120 °C, can be achieved in Ta-modified AgNbO3 ceramics. It is revealed that the incorporation of Ta to the Nb site can enhance the antiferroelectricity because of the reduced polarizability of B-site cations, which is confirmed by the polarization hysteresis, dielectric tunability, and selected-area electron diffraction measurements. Additionally, Ta addition in AgNbO3 leads to decreased grain size and increased bulk density, increasing the dielectric breakdown strength, up to 240 kV cm-1 versus 175 kV cm-1 for the pure counterpart, together with the enhanced antiferroelectricity, accounting for the high energy storage density.
571 citations
TL;DR: In this article, a hybridization between the Bi 6p and O 2p orbitals was proposed to improve the recoverable energy density (Wrec) of lead-free bulk ceramics.
Abstract: The development of lead-free bulk ceramics with high recoverable energy density (Wrec) is of decisive importance for meeting the requirements of advanced pulsed power capacitors toward miniaturization and integration. However, the Wrec (<2 J cm−3) of lead-free bulk ceramics has long been limited by their low dielectric breakdown strength (DBS < 200 kV cm−1) and small saturation polarization (Ps). In this work, a strategy (compositions control the grain size of lead-free ceramics to submicron scale to increase the DBS, and the hybridization between the Bi 6p and O 2p orbitals enhances the Ps) was proposed to improve the Wrec of lead-free ceramics. (K0.5Na0.5)NbO3–Bi(Me2/3Nb1/3)O3 solid solutions (where Me2+ = Mg and Zn) were designed for achieving large Ps, and high DBS and Wrec. As an example, (1 − x)(K0.5Na0.5)NbO3–xBi(Mg2/3Nb1/3)O3 (KNN–BMN) ceramics were prepared by using a conventional solid-state reaction process in this study. Large Ps (41 μC cm−2) and high DBS (300 kV cm−1) were obtained for 0.90KNN–0.10BMN ceramics, leading to large Wrec (4.08 J cm−3). The significantly enhanced Wrec is more than 2–3 times larger than that of other lead-free bulk ceramics. The findings in this study not only provide a design methodology for developing lead-free bulk ceramics with large Wrec but also could bring about the development of a series of KNN-based ceramics with significantly enhanced Wrec and DBS in the future. More importantly, this work opens a new research and application field (dielectric energy storage) for (K0.5Na0.5)NbO3-based ceramics.
439 citations