Mn- and Yb-Doped BaTiO3-(Na0.5Bi0.5)TiO3 Ferroelectric Relaxor with Low Dielectric Loss.

In this work, a Mn-and Yb-doped BaTiO3-(Na0.5Bi0.5)TiO3 ferroelectric relaxor was designed and prepared. The effects of Mn on the microstructures, dielectric and electrical properties of the ceramics were investigated. The X-ray structural analysis shows a perovskite structure. The SEM images show the homogeneous microstructure of ceramics with an average grain size of about 1 µm. The temperature-dependent permittivity shows relaxor characteristics as Mn-doped. Mn at a low level (x ≤ 0.005) is beneficial for low dielectric loss and high resistivity. The maximum resistivity of ≥3 × 1012 Ω cm and minimum dielectric loss of ≤0.06 can be achieved at x ≤ 0.005. The resistivity of the ceramics follows the Arrhenius law with activation energy decreasing from ~1.31 to 1.01 eV as x increases. With lower Mn dopant, oxygen vacancies and charge carrier concentration partially decrease with Mn doping, which is helpful to improve the insulation resistance and decrease the dielectric loss.

Ag2Mo2O7: an oxide solid-state Ag+ electrolyte.

Ag2Mo2O7 powders and micro-crystals were prepared at 400 °C for 24 h and 500 °C for 6 h using solid-state reactions. The Ag2Mo2O7 samples crystalized in a triclinic P1̄ space group with the cell parameters a = 6.0972(1) Å, b = 7.5073(1) Å, c = 7.6779(2) Å, α = 110.43(1)°, ß = 93.17(1)°, γ = 113.51(1)°, and V = 294.17(1) Å3 from Rietveld refinements. Ag2Mo2O7 powder is homogeneous with size of 2-8 µm and the ceramic pellets are in good sintering conditions with a relative density ∼93%. The indirect band gaps E g(i) of Ag2Mo2O7 from reflectance measurements and DFT calculations are 2.63(1) and 1.80 eV. The vibrational modes of Ag2Mo2O7 were investigated by first-principles (DFT) calculations and Raman spectrum measurements with 24 of 33 predicted Raman modes recorded. According to DOS analyses, the valence bands (VB) of Ag2Mo2O7 are mainly constituted of O-2p and Ag-4d orbitals, while the conduction bands (CB) are mainly composed of Mo-4d and the O-2p orbitals. Regarding the impedance analysis, Ag2Mo2O7 is a silver oxide ion electrolyte with a conductivity of ∼5 × 10-4 S cm-1 at 450 °C. The carrier activation energy of Ag2Mo2O7 is 0.88(3) eV from the temperature dependent conductivity measurements.

Structure and Dielectric Behavior of Yb2O3-MgO Co-Doped 0.92BaTiO3-0.08(Na0.5Bi0.5)TiO3 Ferroelectric Relaxor.

Dielectric properties and structure of 0.015Yb2O3-xMgO doped 0.92BaTiO3-0.08(Na0.5Bi0.5)TiO3 ceramics with x = 0.0-0.025 have been investigated. As Yb2O3-MgO was added into the BT-NBT, the phase changes from tetragonal to pseudo-cubic, with the tetragonality c/a decreases from 1.011 to 1.008 and XRD peaks broadened. The combined study of XRD and TEM image revealed a formation of core-shell structure in grains with core of 400-600 nm and the shell of a thickness 60-200 nm. There is a slowly phase transition against temperature from the variable temperature Raman analysis. The ferroelectric relaxor peak of BT-NBT decreases from ~4000 to ~2000 and a new broad dielectric peak with an equivalent maximum (εr'~2300) appears in the temperature dependent dielectric constant curve (εr'-T), which produces a flat εr'-T curve. Sample 0.92BaTiO3-0.08(Na0.5Bi0.5)TiO3-0.015Yb2O3-0.005 MgO and 0.92BaTiO3-0.08(Na0.5Bi0.5)TiO3-0.015Yb2O3-0.01MgO give a εr' variation within ±14% and ±10% in 20-165 °C. The core-shell microstructure should take account for the flattened εr'-T behavior of these samples.

Structure Evolution of Na2O2 from Room Temperature to 500 °C.

Na2O2 is one of the possible discharge products from sodium-air batteries. Here, we report the evolution of the structure of Na2O2 from room temperature to 500 °C using variable-temperature neutron and synchrotron X-ray powder diffraction. A phase transition from α-Na2O2 to ß-Na2O2 is observed in the neutron diffraction measurements above 400 °C, and the crystal structure of ß-Na2O2 is determined from neutron diffraction data at 500 °C. α-Na2O2 adapts a hexagonal P62m (no. 189) structure, and ß-Na2O2 adapts a tetragonal I41/acd (no. 142) structure. The thermal expansion coefficients of α-Na2O2 are a = 2.98(1) × 10-5 K-1, c = 2.89(1) × 10-5 K-1, and V = 8.96(1) × 10-5 K-1 up to 400 °C, and a ∼10% volume expansion occurs during the phase transition from α-Na2O2 to ß-Na2O2 due to the realignment/rotation of O22- groups. Both phases are electronic insulators according to DFT calculations with band gaps (both indirect) of 1.75 eV (α-Na2O2) and 2.56 eV (ß-Na2O2). An impedance analysis from room temperature to 400 °C revealed a significant enhancement of the conductivity at T ≥ 275 °C. α-Na2O2 shows a higher conductivity (∼10 times at T ≤ 275 °C and ∼3 times at T > 275 °C) in O2 compared to in Ar. We confirmed, by dielectric analysis, that this enhanced conductivity is dominated by ionic conduction.

Dielectric properties of lead-free BZT-KNN perovskite ceramics for energy storage.

Lead-free (1-x)Ba(Zr0.15Ti0.85)O3-x(K0.5Na0.5)NbO3 ; x=0-0.05) (BZT-KNN) perovskite ceramics, a materials with potential applications for energy storage, are investigated. The samples are prepared by a solid-state reaction method. Powder X-ray diffraction (XRD) and scanning electron microscopy (SEM) are used to study the microstructure of the samples. Their dielectric properties and impedance spectra are reported as functions of temperature and frequency. The addition of 1 mol % (K0.5Na0.5)NbO3 to Ba(Zr0.15Ti0.85)O3 improves the dielectric constant and enhances its diffuseness in a wide temperature range. The small amount of (K0.5Na0.5)NbO3 is found to markedly affect the microstructure of the Ba(Zr0.15Ti0.85)O3 ceramic (grain size and other characteristics) without changing the phase or crystal symmetry. In addition, we report that fine substructures in the grains, so-called sheet structures, are responsible for the dielectric properties (both diffuseness and dielectric constant) of (1-x)Ba(Zr0.15Ti0.85)O3-x(K0.5Na0.5)NbO3 (x=0-0.03; especially x=0.01) ceramics.