Phase,domain, and microstructures in Sr2+ substituted low-temperature sintering PZT-based relaxor ferroelectrics

The Ag-Pd internal electrode of multilayer piezoelectric ceramics needs to be sintered below 1000°C, and lead wires and components need to be welded with lead-free solder at 260°C. PNN–PMW–PZT–xSr piezoelectric ceramics with high Curie temperature (T_c > 260°C) were synthesized at a low sintering temperature (960°C) to meet the requirements of multilayer piezoelectric devices. The relationship between structures (phase, domain, and microstructures) and electrical properties (piezo/ferroelectric properties, and dielectric relaxation) in the Sr²⁺ substituted ceramics was investigated. Rietveld refinement and Raman spectra show that Sr²⁺ substitution can cause the phase change and increase the force constant of [BO₆] octahedron. The piezoelectric response increases with increasing the content of the tetragonal phase (CTP) in the rhombohedral-tetragonal (R-T) coexisted ceramics. The ceramics with 0.6 mol% Sr²⁺ substitution have minimum activation energy for domain wall movement (E_a) of 0.0362 eV which favors the formation of nanometer-sized domains, and possess excellent electrical properties (d₃₃ = 623 pC/N, d₃₃^* =783 pm/V, T_c =295°C). The higher the CTP, the lower the E_a. The lower E_a favors the rotation of polarization direction and extension, and is beneficial to the generation of the nanometer-size domains, resulting in high piezoelectric properties.     

Influence of the stoichiometry,microstructure, and metallization method on the dielectric properties of 0.94 Na0.5Bi0.5TiO3-0.06 BaTiO3

The morphotropic composition of the lead-free solid solution between Na_0.5Bi_0.5TiO₃ and BaTiO₃ (0.94 Na_0.5Bi_0.5TiO₃-0.06 BaTiO₃ or NBT-6BT) is of particular interest for the next generation of high-temperature capacitors but remains plagued by the diversity of dielectric properties reported in the literature. In order to explain the apparent inconsistencies among the reported dielectric properties of NBT-6BT, we examine the influence of stoichiometry, phase separation, and metallization method. We show that the nominal stoichiometry has a crucial effect, since increasing the nominal Na/Bi ratio increases conductivity and dielectric losses (tan δ). It also increases the real part of the permittivity (ε’) and the frequency dispersion of both ε’ and tan δ, thereby altering the shape of the evolution with temperature of the dielectric properties. Moreover it increases the depolarization temperature (T_d) and decreases the temperature of maximum permittivity (T_m). Phase separation also occurs during the synthesis of NBT-6BT as Na evaporation leads to the formation of secondary Ba-containing phases. We report that these phases can have a positive impact on the dielectric properties: a moderate volume fraction (2.5 to 3.0%) and average grain surface (0.9 to 3.0 µm²) of these secondary Ba-containing phases increase the relative permittivity, decrease the dielectric losses, and increase the insulation resistance. We also show that the metallization method impacts the dielectric properties and therefore may contribute to the differences between various reports. The dielectric properties of NBT-6BT samples are measured during successive heating/cooling cycles and reveal that the permittivity value is lower during the first heating when silver paste, even cured, is used. These three components contribute to explaining the diversity of the reported dielectric properties of NBT-6BT.     

Analysis and proposition of limiting current density measurement protocol

Limiting current density at different temperatures, backpressures, and balance gases can be used to separate molecular diffusion resistance, Knudsen diffusion resistance and local transport resistance of membrane electrode assembly (MEA). However, the measurement of limiting current density has no unified protocol. The diverse choices in the literature, either in the control of current or voltage or in the atmosphere like relative humidity and O₂ concentrations, make it difficult to compare the results and identify the true bottleneck hindering the mass transport. In this work, the current-voltage curves obtained by current scanning/stepping and voltage scanning/stepping methods under dilute O₂ of different concentrations and a wide range of relative humidity were measured and analyzed systematically. It is found that the voltage stepping method is superior to the other three ways of control for the reliable determination of the limiting current density. Aided with simultaneous electrochemical impedance spectroscopy measurement, the limiting current density can be determined with pinpoint accuracy. When the limiting current density is just used to qualitatively evaluate different MEA, the voltage scanning method can be used instead for its high time efficiency. The selection of the atmosphere also plays an important role in suppressing the distortion from excessive water and reducing the spurious contribution from proton conduction resistance. It is found that O₂ concentrations at 0.5 vol% and relative humidity at 90% can give the best estimation of O₂ transport resistance in membrane electrode assembly.     

A-site Ca2+ substitution induced polyvalent Cu cations and correlated polaron relaxations in colossal permittivity Li1-xCaxCuNb3O9

LiCuNb₃O₉ has been reported newly a colossal permittivity (CP) perovskite, in which the B-site NbO₆ octahedra play a bridging role in the polaron hopping. However, how the A-site modification affects the origin of the polarons and further the CP behaviours remains unexplored. To this end, A-site Ca²⁺ was incorporated to form Li_1-xCa_xCuNb₃O₉, and the local states, dielectric relaxations and conduction behaviours were comprehensively studied. The substitution induces the polyvalent Cu cations, i.e. Cu⁺/Cu²⁺/Cu³⁺. Bond valence sum calculations imply that Cu²⁺ and Cu³⁺ are underbonded, and Cu⁺ is overbonded, while B-site Nb⁵⁺ shows slightly different with theoretical pentavalence. All the compositions exhibit a similarly room-temperature CP response, but present two dielectric relaxations, i.e. T_R1:170–300 K and T_R2:260–400 K. Comprehensive investigations on universal dielectric response and bulk dc conductivity indicate that the T_R1 follows the variable-range-hopping where the electron hopping between the mixed Cu⁺/Cu²⁺, while T_R2 contributes from the Cu³⁺ nearest neighbor hopping.     

Influence of Sr ions on the structure and dielectric properties of Cu/Nb Co-doped BaTiO3 ceramics

Sr-modified Cu/Nb co-doped BaTiO₃ ceramics were prepared using solid-state reactions and the structures and dielectric properties were studied. All the samples had single-phase perovskite structures with no detectable secondary phases. In the low-temperature range, the dielectric constant decreased as the Sr content increased in the high- and low-frequency ranges. Two dielectric constant plateaus accompanied by dielectric relaxation peaks were present in the loss curves, and the relaxation process deviated from the Arrhenius law at low temperatures. The dielectric constants of different plateaus were related to inhomogeneous structures such as grain interiors and grain boundaries. The polarization strength of the grain boundaries in the low-frequency range increased with the temperature and that of the grain interiors demonstrated paraelectric behaviour in high-temperature ranges. An analysis of the electric modulus spectra indicated a close relationship between the relaxation process and resistivity of the grains for high-frequency relaxation. The impedance spectra at high temperatures consist of three electrical responses, corresponding to the effects of grains, grain boundaries, and electrodes. The dielectric relaxation appeared in high temperature range was related to the electrical properties of the grain boundaries.     

Microcrack healing in zirconia ceramics under a DC electric field/current

Flash event caused by a DC electric field/current was applied to the crack healing in 8 mol % Y₂O₃ stabilized cubic ZrO₂ polycrystals (8Y-CSZ). The flash event, which occurred by applying the DC power higher than a critical value of 100 mW/mm³, successfully healed the microcrack within several minutes without any healing agents at a furnace temperature of 800 °C. As compared to the healing treatment under static annealing, the healing phenomena were accelerated about 2 times under the flash treatment even at the same temperatures, suggesting that the enhanced healing phenomena cannot be explained only by the temperature effect. Since the rate of grain growth was accelerated under the flash treatment, the flash healing would be accelerated through the current-enhanced diffusional processes. This study shows for the first time that the flash event has a potential to apply to the crack healing process in the ceramic materials and composites.     

FeOOH–CoS composite catalyst with high catalytic performances for oxygen evolution reaction at high current density

Water electrolysis is an efficient approach for high-purity hydrogen production. However, the anodic sluggish oxygen evolution reaction (OER) always needs high overpotential and thus brings about superfluous electricity cost of water electrolysis. Therefore, exploiting highly efficient OER electrocatalysts with small overpotential especially at high current density will undoubtedly boost the development of industrial water electrolysis. Herein, we used a simple hydrothermal method to prepare a novel FeOOH–CoS nanocomposite on nickel foam (NF). The as-prepared FeOOH–CoS/NF catalyst displays an excellent OER performance with extremely low overpotentials of 306 and 329 mV at 500 and 1000 mA cm⁻² in 1.0 M KOH, respectively. In addition, the FeOOH–CoS/NF catalyst can maintain excellent catalytic stability for more than 50 h, and the OER catalytic activity shows almost no attenuation no matter after 1000 repeated CV cycles or 50 h of stability test. The high catalytic activity and stability have exceeded most non-noble metal electrocatalysts reported in literature, which makes the FeOOH–CoS/NF composite catalyst have promising applications in the industrial water electrolysis.     

Influence of anode current density on carbon parasitic reactions during electrolysis

In the electro-deoxidation process, carbon parasitic reaction (CO₃^2- + 4e^-=C + 3O^2-) usually occurs when using carbon materials as the anode, which leads to increase of the carbon content in the final metal and decrease of the current efficiency of the process. The aim of this work is to reduce the negative effect of carbon parasitic reaction on the electrolysis process by adjusting anode current density. The results indicate that lower graphite anode area can achieve higher current density, which is helpful to increase the nucleation site of CO₂ bubbles. Most of CO₂ would be released from the anode instead of dissolution in the molten CaCl₂ and reacting with O^2- to form CO₃^2-, thus decreasing the carbon parasitic reaction of the process. Furthermore, the results of the compared experiments show that when the anode area decreases from 172.78 to 4.99 cm², CO₂ concentration in the released gases increases significantly, the carbon mass content in the final metal product decreased from 1.09% to 0.13%, and the current efficiency increased from 6.65% to 36.50%. This study determined a suitable anode current density range for reducing carbon parasitic reaction and provides a valuable reference for the selection of the anode in the electrolysis process.     

Large electrostrictive effect and high energy storage performance of Pr3+-doped PIN-PMN-PT multifunctional ceramics in the ergodic relaxor phase

The photoluminescence, dielectric relaxation, ferroelectric hysteresis, and field-induced strain properties of Pr³⁺-doped 0.24Pb(In_1/2Nb_1/2)O₃-0.42Pb(Mg_1/3Nb_2/3)O₃-0.34PbTiO₃ (PIN-PMN-PT:Pr³⁺) multifunctional ceramics have been investigated. It was found that Pr³⁺ doping enhanced the dielectric diffuseness and relaxation behavior of PIN-PMN-PT ceramics. Slim P-E loops and S-E curves appear in PIN-PMN-PT:Pr³⁺ ceramics when the Pr³⁺ doping concentration reaches 1.4 mol%. Local domain configurations associated with phase transitions were investigated by piezoresponse force microscopy (PFM). Large electrostrictive coefficient Q₃₃ (?0.03 m⁴/C²) and high energy-storage efficiency η (92%) were obtained in 2 mol% Pr³⁺-doped PIN-PMN-PT ceramic in the ergodic relaxor (ER) phase at room temperature. The giant electrostrictive effect and excellent energy-storage performance are related to the field-induced dynamic behavior of polar nanoregions (PNRs). The results show that the PIN-PMN-PT:Pr³⁺ system is an excellent multifunctional material for making electromechanical and energy storage devices.