Review on zirconate-cerate-based electrolytes for proton-conducting solid oxide fuel cell

The performance of low-to-intermediate temperature (400–800?°C) solid oxide fuel cells (SOFCs) depends on the properties of electrolyte used. SOFC performance can be enhanced by replacing electrolyte materials from conventional oxide ion (O^2-) conductors with proton (H⁺) conductors because H⁺ conductors have higher ionic conductivity and theoretical electrical efficiency than O^2- conductors within the target temperature range. Electrolytes based on cerate and/or zirconate have been proposed as potential H⁺ conductors. Cerate-based electrolytes have the highest H⁺ conductivity, but they are chemically and thermally unstable during redox cycles, whereas zirconate-based electrolytes exhibit the opposite properties. Thus, tailoring the properties of cerate and/or zirconate electrolytes by doping with rare-earth metals has become a main concern for many researchers to further improve the ionic conductivity and stability of electrolytes. This article provides an overview on the properties of four types of cerate and/or zirconate electrolytes including cerate-based, zirconate-based, single-doped cerate–zirconate and hybrid-doped cerate–zirconate. The properties of the proton electrolytes such as ionic conductivity, chemical stability and sinterability are also systematically discussed. This review further provides a summary of the performance of SOFCs operated with cerate and/or zirconate proton conductors and the actual potential of these materials as alternative electrolytes for proton-conducting SOFC application.     

液相沉淀-煅烧法制备大粒径球形四氧化三钴

以硫酸钴为原料,碳酸氢铵为沉淀剂,采用液相沉淀法合成了大粒径球形碳酸钴,考察了不同晶种量、pH和硫酸钴溶液流量对碳酸钴形貌、粒度分布、振实密度和硫元素质量分数的影响,并探究了碳酸钴的生长机理。通过分步煅烧,并设置不同升温时间使碳酸钴热分解,得出优化四氧化三钴理化指标的煅烧条件。结果表明,当晶种量为2 kg,pH在7.2～7.5,硫酸钴溶液流量为500 mL/h时,采用分段式热分解碳酸钴,各温区按统一时间(60 min)升温,所得四氧化三钴形貌为球形,中值粒径为16.52μm,振实密度达2.26 g/cm3。     

Novel nanometer alumina-silica insulation board with ultra-low thermal conductivity

Advanced nano-porous super thermal insulation materials are widely used in spacecraft, soler-thermal shielding, heat exchangers, photocatalytic carriers due to their low thermal conductivity. In this work, adopting dry preparation technology, nano-Al₂O₃, nano-SiO₂, SiC and glass fibers as raw materials, novel nanometer alumina-silica insulation board (NAIB) were prepared. The preparation process was simple, safe, and reliable. In addition, the NAIB exhibited a high porosity (91.3–92.3%), small pore size (39.83–44.15 nm), low bulk density (0.22–0.26 g/cm³), better volumetric stability, and low thermal conductivity (0.031–0.050 W/(m·K) (200–800 °C)), respectively. The as-prepared NAIB could render them suitable for application as high-temperature thermal insulation materials.     

Tailoring the chemical heterogeneity of Mn-modified 0.75BiFeO3-0.25BaTiO3 ceramics for piezoelectric sensor applications

The Mn-modified 0.75BiFeO₃-0.25BaTiO₃ (75BFBTMn) piezoelectric ceramic possesses a high depolarization temperature of 500 °C and a large piezoelectric coefficient of 110 pC/N, showing the potential for high temperature piezoelectric sensors. However, 75BFBTMn ceramic usually suffers dielectric degradation and abrupt drop of piezoelectric coefficient in the range of 300 °C to 500 °C. Combined the high-energy synchrotron X-ray diffraction analysis with Backscatter-SEM results, it is demonstrated that the electrical thermal instability is owing to the existence of chemical inhomogeneity. The Air-annealing treatment is able to decrease the volume fraction of pseudo-cubic phase and the lattice distortion, removes the chemical inhomogeneity in the grain and free Bi₂O₃ at grain boundary, and then eliminates dielectric anomalies and piezoelectric degradation with temperature. These results indicate that air-annealing is a simple but effective method to eliminate the chemical inhomogeneity in 75BFBTMn ceramics, thereby improving the property thermal stability for high temperature piezoelectric sensor applications.     

Characterization of anisotropic gas permeability and thermomechanical properties of highly textured porous alumina

Porous alumina with a highly textured microstructure was fabricated by pulse electric current sintering (PECS) using alumina platelets. Highly oriented porous alumina with a porosity of 3%–50% was obtained by a pressure-controlled method of PECS. The properties of the highly textured porous alumina were measured in two directions. The nitrogen gas permeance and thermal conductivity at room temperature were higher in the direction along the platelet length due to the higher continuity of pores and the connectivity of alumina platelets, respectively. The anisotropy of the thermal conductivity at room temperature was investigated and explained by the effect of grain size of platelets as well as morphology and orientation of pores. The bending strength was higher with the loading direction along the platelet thickness. The thermal shock strength was clearly different in the two directions. The difference in the thermal shock strength was investigated by the measurement of properties and thermal stress analysis.     

Synergistic effect of binary fluoride sintering additives on the properties of silicon nitride ceramics

A variety of combinations of YF₃ and MgF₂ were used as sintering aids in the fabrication of Si₃N₄ ceramics via gas pressure sintering (GPS). The synergistic effects of YF₃ and MgF₂ on the liquid viscosity, mechanical properties, thermal conductivities, and grain growth kinetics of the Si₃N₄ ceramics were investigated. The results showed that appropriately adjusting the YF₃/MgF₂ ratio could decrease liquid viscosity, reducing the diffusion energy barrier of the solute atom and promoting mass transfer. Meanwhile, the chemical bonding strength in the grain boundary complexions formed by the metal cations also influenced grain boundary migration. Samples doped with 4 mol% YF₃ and 2 mol% MgF₂ achieved the lowest grain growth exponent (n = 2.9) and growth activation energy (Q = 616.7 ± 16.5 kJ mol^?1) as well as the highest thermal conductivity (83 W m^?1 K^?1) and fracture toughness (8.82 ± 0.13 MPa m^1/2).     

Grain boundary engineered,multilayer graphene incorporated LaCoO3 composites with enhanced thermoelectric properties

Enhancement of thermoelectric properties by virtue of decreased electrical resistance through grain boundary engineering is realised in this study. A robust strategy of optimisation of the transport properties by tuning the energy filtering effects at the interfaces by decreasing the interfacial electrical resistance is achieved in LaCoO₃ (LCO). This is accomplished by the incorporation of multilayer graphene within the parent LCO matrix containing multi-scale nano/micro grains. The present work has attained a substantial increment in electrical conductivity from a value of 96 Scm^-1 for bare LCO to ～5300 Scm^-1 at 750 K by incorporating 0.08 wt% multilayer graphene in LCO. No significant change in thermal conductivity is observed due to the presence of multilayer graphene in LCO. A zT of 0.33 at 550 K for 0.08 wt% multi-layer graphene incorporated LCO composite is achieved which is the highest thermoelectric figure of merit value for undoped LCO reported until now.     

Wear-resistant ceramic coatings deposited by liquid thermal spraying

As a surface strengthening and surface modification technology of materials, liquid thermal spray technology has been used in many fields, such as wear and friction reduction, corrosion resistance, and high-temperature oxidation resistance. This article reviews the progress of liquid thermal sprayed coating in wear resistance as well as friction reduction in recent years. The influences of microstructure, composition, phase structure and mechanical properties on the tribological properties of typical coatings (including ceramic coatings and multiphase composite coatings) are investigated. The tribological properties of the coating are determined by the coating characteristics (including microstructure, porosity, mechanical properties, etc.) and the service conditions (working temperature, lubrication state, etc.). Typical ceramic wear-resistant coatings include Al₂O₃, YSZ, HA coatings, etc. The tribological properties of the coating can be significantly improved through process optimization and heat treatment. The comparison of nanostructured and microstructured ceramic-based coating reveals that nanostructured coating reduces wear by absorbing stress. The interaction between different constituent phases improves wear resistance and reduces wear in composite coatings. Finally, various challenges faced by liquid thermal spray are pointed out, and future research focuses are proposed.     

Bi2O3–Nd2O3–WO3 system: Phase formation,polymorphism, and conductivity

Cubic, tetragonal, and monoclinic (Bi₂O₃)_x (Nd₂O₃)_y (WO₃)_z (x + y + z = 1) solid solutions based on the Bi₂O₃ oxygen ion conductor have been prepared by solid-state reactions in the ternary system Bi₂O₃–Nd₂O₃–WO₃. The field of monoclinic compounds with a Bi_3·24La₂W_0·76O_10.14-type structure has been shown to account for most of the ternary system. Compounds with a cubic fluorite structure exist at the boundary of the monoclinic phase field in two small regions at high (83–91 mol% Bi₂O₃, δ-phase) and low (20–55 mol% Bi₂O₃, δ′-phase) Bi concentrations. The cubic samples of the δ-phase retain their structure only during rapid heating and cooling, but annealing in the range of 300–700 °C results in structure degradation to lower symmetry phases. The monoclinic compounds and Bi-poor cubic compounds (δ′-phase) have good thermal stability. The cubic samples of the δ′-phase are hygroscopic. Their bulk conductivity noticeably increases with atmospheric humidity, suggesting that these materials are potential proton conductors.     

High-entropy ferroelastic rare-earth tantalite ceramic: (Y0.2Ce0.2Sm0.2Gd0.2Dy0.2)TaO4

In this study, high-entropy rare-earth tantalate ceramics (Y_0.2Ce_0.2Sm_0.2Gd_0.2Dy_0.2)TaO₄ ((5RE_0.2)TaO₄) have been successfully fabricated. The possibility of formation of (5RE_0.2)TaO₄ was verified via first-principles calculations. In addition, the phase structure, ferroelastic toughening mechanism, thermophysical, and mechanical properties were systematically investigated. The (5RE_0.2)TaO₄ ceramics have lower phonon thermal conductivity (1.2–2.6 W·m^–1·K^–1) in the entire temperature range than that of RETaO₄ and YSZ. (5RE_0.2)TaO₄ has a higher fracture toughness and lower brittleness index than YSZ. The thermal expansion coefficients of (5RE_0.2)TaO₄ are as high as 10.3 × 10^-6 K^–1 at 1200°C and Young's modulus is 66–189 GPa, and thus, (5RE_0.2)TaO₄ possesses great potential for application in thermal barrier coatings (TBCs).