The effect of rare-earth oxides on the energy storage performances in BaTiO3 based ceramics

In this work, 0.7BaTiO₃-0.3Sr_0.2Bi_0.7TiO₃ (0.7BT-0.3SBT) ceramics with 0.15 mol% various rare-earth oxides doped are designed and synthesized by the conventional solid-state route. All prepared samples exhibited a single perovskite phase and dense microstructure with fine grain size (0.2–0.5 μm) after sintering at 1180 °C. Especially, the Gd-doped 0.7BT-0.3SBT ceramics exhibited excellent energy storage performances; the corresponding recoverable energy density and efficiency were 3.2 J/cm³ and 91.5% under an electric field of 330 kV/cm, respectively. Meanwhile, doping with Gd caused the BT-based ceramics to possess excellent temperature (30–150 °C) and outstanding frequency stabilities (10–1000 Hz). Moreover, the pulsed charge-discharge experiments revealed that a high power density of 59 MW/cm³ and a fast discharge speed of 110 ns with outstanding temperature stability could be synchronously obtained in the Gd-doped composition. All these features are attractive for pulsed power applications.     

Intrinsic Defect Limit to the Growth of Orthorhombic HfO2 and (Hf,Zr)O2 with Strong Ferroelectricity: First-Principles Insights

It is believed that promoting the fraction of ferroelectric orthorhombic phase (o-phase) through O-poor growth conditions can increase the spontaneous polarization of HfO₂ and (Hf,Zr)O₂ thin films. However, the first-principles calculations show that the growth may be limited by the easy formation of point defects in the orthorhombic and tetragonal phases of HfO₂, ZrO₂, and (Hf,Zr)O₂. Their dominant defects, O interstitial (O_i) under O-rich conditions and O vacancy (V_O) under O-poor condition, have low formation energies and quite high density (10¹⁶–10¹⁹ cm⁻³ for 800–1400 K growth temperature). Especially, O_i has negative formation energy in tetragonal HfO₂ under O-rich condition, causing non-stoichiometry and limiting the crystalline-seed formation during o-phase growth. High-density defects can cause disordering of dipole moments and increase leakage current, both diminishing the polarization. These results explain the experimental puzzle that the measured polarization is much lower than the ideal value even in O-poor thin films and highlight that controlling defects is as important as promoting the o-phase fraction for enhancing ferroelectricity. The O-intermediate condition (average of O-rich and O-poor conditions) and low growth temperature are proposed for fabricating HfO₂ and (Hf,Zr)O₂ with fewer defects, lower leakage current, and stronger ferroelectricity, which challenges the belief that O-poor condition is optimal.     

Surface structure and quenching effects in BiFeO3-BaTiO3 ceramics

The structure and properties of Mn-doped 0.67BiFeO₃-0.33BaTiO₃ ceramics are systematically investigated with respect to the effects of annealing prior to rapid cooling by quenching in air. Air-quenching induces a change in crystal structure from pseudo-cubic to rhombohedral, with higher quenching temperatures leading to an increased rhombohedral distortion. These structural changes are correlated with the appearance of more well-defined ferroelectric domain configurations. It is shown that the surface preparation procedures for XRD measurements can induce significant changes in the peak profiles, indicating differences in crystal structure between the surface and bulk regions. Frequency dispersion in the temperature-dependent relative permittivity for the as-sintered sample is significantly reduced after quenching, accompanied by enhancement of the Curie point and improved temperature-stability of piezoelectric properties. It is proposed that the formation of defect clusters by A-site cation diffusion during cooling is circumvented by quenching, leading to the observed modification of structural distortion and ferroelectric properties.     

Improved energy storage density and energy efficiency of Samarium modified PMNT electroceramic

We report the improved energy storage density and efficiency after 2.5% of Samarium substitution in ferroelectric Pb[(Mg_1/3Nb_2/3)_0.80Ti_0.20]O₃ (PMNT) electroceramic. The microstructure and surface morphology were analyzed and correlated with various functional properties. The energy storage density, leakage current density, ferroelectric and dielectric properties were investigated thoroughly, indicating that Samarium's substitution significantly modified the microstructure, the dielectric strength, breakdown electric field, and turned ferroelectric PMNT to relaxor ferroelectrics. Due to the relaxor nature, the gap between remanent polarization and maximum polarization increases with the substitution of Samarium in PMNT matrix, which further increases the recoverable energy storage density and energy efficiency. A nearly 100% increase in recoverable energy density and efficiency was obtained at an electric field strength of 35 kV/cm at room temperature (～296 K). The electroceramic shows maximum energy density near the ferroelectric phase transition temperature (325 K–345 K) region and provides a moderate energy storage density for possible applications in power microelectronics.     

Relaxor behavior and energy storage density induced by B-sites substitutions in (Ca0.28Ba0.72)2.1Na0.8Nb5O15 Tungsten bronze ceramics

Lead-free relaxor ferroelectrics (Ca_0.28Ba_0.72)_2.1Na_0.8Nb_5-xSb_xO₁₅ (CBNNS) and (Ca_0.28Ba_0.72)_2.1Na_0.8Nb_5-yTa_yO₁₅ (CBNNT) with tungsten bronze structure were fabricated via solid-state reactions. The obtained CBNNS and CBNNT ceramics showed different dielectric behaviors. Only the CBNNS ceramics revealed an intensified diffusion and relaxor-like characteristics, which could be verified by the modified Curie–Weiss law. The relaxor behaviors in CBNNS were attributed to the radii difference between Sb⁵⁺ and Nb⁵⁺ ions co-occupying in B-sites. For the substitution of Nb⁵⁺ by Sb⁵⁺ in CBNNS ceramics, the change from macroscopic polarization to local polarization could also give rise to the obvious relaxor behavior. The Raman spectra verified a larger off-centering of the cation and a higher distortion degree for BO₆ octahedron in the ab plane for CBNNS ceramics when compared with those of CBNNT. In addition, the ferroelectric properties of CBNNS ceramics further indicated the relaxor ferroelectric nature, and also confirmed that the relaxor behavior helped to improve the energy-storage performance.     

GeTe中铁电极化对自旋霍尔电导的调控研究

利用电场控制电荷的自旋流与电流相互转换是自旋电子器件的关键所在,而这种控制机制在铁电半导体GeTe中可以得到实现,因为其铁电极化可以改变自身的自旋织构。基于密度泛函理论计算,我们发现可以通过铁电极化可以进一步调节自旋霍尔电导(spinHallconductivity,简记为SHC),通过计算得到自旋霍尔电导的一个分量σxyz在带边缘附近可以达到100?/e(?cm)-1的量级,其主要原因在于电极化改变了能带结构。该研究工作为可控的自旋输运的实验和理论研究具有重要的价值,必将推动自旋电子学的进一步发展。     

Fabrication of 0.24Pb(In1/2Nb1/2)O3-0.42Pb(Mg1/3Nb2/3)O3-0.34PbTiO3 transparent ceramics by conventional sintering technique

0.24Pb(In_1/2Nb_1/2)O₃-0.42Pb(Mg_1/3Nb_2/3)O₃-0.34PbTiO₃ transparent ceramics were fabricated by a conventional sintering technique. Through optimization of sintering conditions of calcination and sintering temperatures and time, the obtained ceramics showed high optical transmittance of 53% and 71% at light wavelengths of 1300 and 2000 nm, respectively. The ceramics showed a rhombohedral to tetragonal phase transition at ~120°C and a tetragonal to cubic phase transition at 222°C. These transition temperatures were higher than those of 0.67Pb(Mg_1/3Nb_2/3)-0.33PbTiO₃ ceramics. In addition, the ceramics had a ferroelectric hysteresis loop, a large piezoelectric constant d₃₃ of 407 pC/N, and a planar electromechanical coupling factor k_p of 52%. These results suggest that the transparent ceramics may be used as a temperature-stable, linear electro-optic material.     

Dielectric,ferroelectric, and piezoelectric properties of lead-free Ba0.95Ca0.05Ti1-xZrxO3 ceramics

Abstract

Ba_0.95Ca_0.05Ti_1-xZr_xO₃ (BCTZO) ceramics were prepared by a solid state reaction method. The samples were characterized by X-ray diffraction (XRD), Scanning electron microscopy (SEM) and X-ray absorption near edge structure (XANES). The ceramics exhibit a pure perovskite structure. The average grain size gradually decreases with increasing Zr concentration. XANES results indicate that the intensities of pre-edge peaks dropped with increasing Zr concentration. The BCTZO ceramic of x?=?0.05 has the optimum electrical properties with the maximum dielectric constant (ε'_m), remanent polarization (2P_r), coercive electric field (2E_c) and piezoelectric charge constant (d₃₃) of 7,244, 12.54 (μC/cm²), 5.29 (kV/cm) and 288 (pC/N), respectively.     

Structure development and dielectric properties of Zn-doped Pb([Mg,Fe],W)O3 perovskite ceramics

Ceramic samples of a pseudo-binary system Pb(Mg_1/2W_1/2)O₃-Pb(Fe_2/3W_1/3)O₃ (PMW-PFW) were prepared by solid-state reaction. In addition, their compositions were modified by 20 mol% Pb(Zn_1/2W_1/2)O₃ (PZW) doping in order to investigate the role of zinc in the perovskite formation and dielectric properties. The perovskite contents were ≥95.1% at the overall composition range, except for a significantly low value of 79.0% at 0.8PFW-0.2PZW. The extension of sintering time for PMW accelerated superstructure formation, resulting in the ordering factor increased up to 0.40 after 12 hours heat treatment. The maximum dielectric constant values increased with increasing PFW fractions. In comparison, the phase transition temperatures decreased sharply (by up to 161°C) at low concentrations of PFW, followed by mild changes (by up to 47°C) afterward. The dielectric constant spectra were analyzed in terms of diffuseness characteristics, which reflected the phase transition modes quite well.     

Absence of ferromagnetism in ferroelectric Mn-doped BaTiO3 nanofibers

Pure and Mn-doped barium titanate nanofibers were synthesized by the electrospinning method. The morphology, microstructure and crystal structure of as-spun and annealed composite nanofibers were characterized by scanning electron microscopy and transmission electron microscopy. After annealing at 850°C, we obtain nanofibers a few μm long, formed by nanoparticles of irregular shape with sizes around 100 nm. X-ray diffraction and Raman spectroscopy show that a partial phase transition from tetragonal to hexagonal takes place for BaTi_0.90Mn_0.10O₃. Vibrational phonon modes were calculated for BaTiO₃ within the density functional theory (DFT) framework. Ferroelectricity has been probed on pure and Mn-doped BaTiO₃ nanofibers, by means of piezoresponse force microscopy in an atomic force microscope, confirming the polar domain switching behavior of the fibers. The measured piezoelectric coefficient d₃₃ were 31 and 22 pm/V for BaTiO₃ and BaTi_0.90Mn_0.10O₃. Magnetic properties of the samples were probed in a superconducting quantum interference device. Diamagnetic and paramagnetic behaviors were found in pure and Mn-doped samples, respectively.