One step densification of SDC—Na2CO3 nano-composite electrolytes for SOFC applications by cold sintering process

Sm_0.2Ce_0.8O_1.9- 30% Na₂CO₃ (Sm doped ceria (SDC)-30N) nano-composite electrolytes were densified in a single step via cold sintering process (CSP). At 200°C and 450 MPa of uniaxial pressure, samples up to 97% of their theoretical density could be obtained. The effect of processing parameters, such as temperature, uniaxial pressure, processing duration, and moisture content, on the densification of the nano-composite electrolytes was investigated. The thermal, microstructural, and electrical properties of nano-composites were investigated by differential scanning calorimetry, X-ray diffractometer, scanning electron microscope, and EIS analysis. SDC crystallite sizes were found to be around 25 nm, barely coarsened after CSP by which the true nano nature of the nano-composite could be preserved. Because, by conventional processing high density values could not be attained and high processing temperatures in excess of 600°C had to be used, promoting particle coarsening. The highest total electrical conductivity was found to be 2.2 × 10⁻² S cm⁻¹ at 600°C, with an activation energy of 0.83 eV for SDC-30N nano-composites. The present investigation revealed that the implementation of cold sintering technique resulted in significant enhancements in the densification of nano-composite electrolytes, thereby rendering them suitable for efficient utilization in SOFC applications, as compared to the conventional production methods.     

Direct addition of lithium and cobalt precursors to Ce0.8Gd0.2O1.95 electrolytes to improve microstructural and electrochemical properties in IT-SOFC at lower sintering temperature

To improve the microstructural and electrochemical properties of gadolinium-doped ceria (GDC) electrolytes, materials co-doped with 0.5–2?mol% of lithium and cobalt oxides were successfully prepared in a one-step sol gel combustion synthesis route. Vegard's slope theory was used to predict the dopant solubility and the sintering behaviour. The charge and size of the added dopant influence the atom flux near the grain boundary with a change in the lattice parameter. In fact, compared to traditional multi grinding steps, sol gel combustion facilitates molecular mixing of the precursors and substitution of the dopant cations into the fluorite structure, considerably reducing the sintering temperature. Adding precursors of lithium and cobalt, as dopant, increases the GDC densification and reduces its traditional sintering temperature down to 1000–1100?°C, with an improvement of electrochemical properties. Impedance analysis showed that the addition of 2?mol% of lithium or 0.5?mol% of cobalt enhances the conductivity with a consequent improvement of cell performances. High total conductivities of 1.26·10^?1 S?cm^?1 and 8.72·10^?2 S?cm^?1 at 800?°C were achieved after sintering at 1000?°C and 1100?°C for ²LiGDC and ^0.5CoGDC, respectively.     

Electrical Conductivity of Mullite Ceramics

The electrical conductivity of a lab‐produced homogeneous mullite ceramic sintered at 1625°C for 10 h with low porosity was measured by impedance spectroscopy in the 0.01 Hz to 1MHz frequency range at temperatures between 300°C and 1400°C in air. The electrical conductivity of the mullite ceramic is low at 300°C (≈0.5 × 10^?9 Scm^?1), typical for a ceramic insulator. Up to ≈ 800°C, the conductivity only slightly increases (≈0.5 × 10^?6 Scm^?1 at 800°C) corresponding to a relatively low activation energy (0.68eV) of the process. Above ≈ 800°C, the temperature‐dependent increase in the electrical conductivity is higher (≈10^?5 Scm^?1 at 1400°C), which goes along with a higher activation energy (1.14 eV). The electrical conductivity of the mullite ceramic and its temperature‐dependence are compared with prior studies. The conductivity of polycrystalline mullite is found to lie in‐between those of the strong insulator α‐alumina and the excellent ion conductor Y‐doped zirconia. The electrical conductivity of the mullite ceramic in the low‐temperature field (< ≈800°C) is approximately one order of magnitude higher than that of the mullite single crystals. This difference is essentially attributed to electronic grain‐boundary conductivity in the polycrystalline ceramic material. The electronic grain‐boundary conductivity may be triggered by defects at grain boundaries. At high temperatures, above ≈ 800°C, and up to 1400°C gradually increasing ionic oxygen conductivity dominates.     

A benzoate coprecipitation route for synthesizing nanocrystalline GDC powder with lowered sintering temperature

Electrolyte powders with low sintering temperature and high-ionic conductivity can considerably facilitate the fabrication and performance of solid oxide fuel cells (SOFCs). Gadolinia-doped ceria (GDC) is a promising electrolyte for developing intermediate- and low-temperature (IT and LT) SOFCs. However, the conventional sintering temperature for GDC is usually above 1200 °C unless additives are used. In this work, a nanocrystalline powder of GDC, (10 mol% Gd dopant, Gd_0.1Ce_0.9O_1.95) with low-sintering temperature has been synthesized using ammonium benzoate as a novel, environmentally friendly and cost-effective precursor/precipitant. The synthesized benzoate powders (termed washed- and non-washed samples) were calcined at a relatively low temperature of 500 °C for 6 h. Physicochemical characteristics were determined using thermal analysis (TG/DTA), Raman spectroscopy, FT-IR, SEM/EDX, XRD, nitrogen absorptiometry, and dilatometry. Dilatometry showed that the newly synthesized GDC samples (washed and non-washed routes) start to shrink at temperatures of 500 and 600 °C (respectively), reaching their maximum sintering rate at 650 and 750 °C. Sintering of pelletized electrolyte substrates at the sintering onset temperature for commercial GDC powder (950 °C) for 6 h, showed densification of washed- and non-washed samples, obtaining 97.48 and 98.43% respectively, relative to theoretical density. The electrochemical impedance spectroscopy (EIS) analysis for the electrolyte pellets sintered at 950 °C showed a total electrical conductivity of 3.83 × 10^?2 and 5.90 × 10^?2 S cm^?1 (under air atmosphere at 750 °C) for washed- and non-washed samples, respectively. This is the first report of a GDC synthesis, where a considerable improvement in sinterability and electrical conductivity of the product GDC is observed at 950 °C without additives addition.     

Effect of grain size on the electrical performance of BaZr0.1Ce0.7Y0.1Yb0.1O3-δ solid electrolytes with addition of NiO

In order to clarify the effect of grain size on the electrical performance of BaZr_0.1Ce_0.7Y_0.1Yb_0.1O_3-δ (BZCYYb) solid electrolytes with addition of NiO, microcrystalline (~1.5?µm) and ultrafine-grained (~280?nm) BZCYYb electrolytes (with 1?wt% NiO) were fabricated by the conventional and two-step sintering method, respectively. The results show that compared with microcrystalline electrolytes, the ultrafine-grained electrolytes have similar grain-interior conductivities, but much lower grain-boundary conductivities, illustrating that the grain boundary is not conducive for ionic transport. As a result, the electrical conductivity of microcrystalline electrolytes (1.9?×?10^?2 S?cm^?1 at 600?°C in wet air) is higher than that of ultrafine-grained electrolytes (1.1?×?10^?2 S?cm^?1 at 600?°C in wet air). In addition, the OCV (open-circuit voltage) values of electrolyte-supported single cells show that the undesired electronic conduction exists in the electrolytes due to the BaY₂NiO₅ impurity formed by the reaction of NiO and BZCYYb. The ultrafine-grained electrolytes show lower OCV values than that of microcrystalline ones, due to the prolonged electronic transport paths. Therefore, large-grained or grain boundary-free microstructure are necessary for improving the electrical performance of BZCYYb electrolytes.     

Influence of the precursor pyrolysis temperature on the microstructure and conductivity of Gd-doped ceria materials

Gd-doped ceria nanopowders have been synthesized via a modified sol–gel technique using different pyrolysis temperatures to produce a range of particle sizes. Such nanocrystalline oxides have been sintered at 1400 °C for 24 h to produce fully dense disks. The microstructural characterization reveals that the pyrolysis temperature notably affects the grain size distribution in the sintered ceramics, e.g. powders treated at 700 °C render the narrowest grain size distribution. The electrochemical characterisation performed by electrochemical impedance spectroscopy shows that the distribution of grain sizes in the dense electrolytes rules the electrical conductivity of CGOs rather than the average grain size. Narrower grain size distributions render electrolytes exhibiting higher overall conductivity, independent of the average grain size.     

Low temperature densification by lithium co-doping and its effect on ionic conductivity of samarium doped ceria electrolyte

Low temperature densification and improving the ionic conductivity of doped ceria electrolyte is important for the realization of efficient intermediate temperature solid oxide fuel cell system. Herein, we report the effect of lithium co-doping (1, 3, 5 and 7?mol%) in 20?mol% samarium doped ceria on the low temperature sinterability and conductivity. The synthesized nanoparticles by citrate-nitrate combustion method showed a decrease in lattice parameter and increase in oxygen vacancy with lithium content after calcination due to the substitution of Li⁺ into CeO₂ lattice. Upon sintering at 900?°C, the density improved and reached a maximum value of 98.6% for 5% Li which exhibited a dense microstructure than at 7% Li. 5%Li co-doping exhibited the best conductivity of 3.65?×?10^?04–1.81?×?10^?3 S?cm^?1 in the operative temperature range of IT-SOFC (550–700?°C).Our results demonstrate the significance of lithium as co-dopant for efficient low temperature sintering as well as improving the electrolyte conductivity.     

Optimal sintering parameters for Al2O3 optoceramics with high transparency by spark plasma sintering

Transparent Polycrystalline Alumina (PCA) optical ceramics were fabricated at a high heating rate and low temperature by spark plasma sintering (SPS). Maximum pressure (100?MPa) at dwell time keeps the grain size small irrespective of the dwell time. A heating and cooling rate of 100°C?min^?1 at the sintering temperature of 1150°C for a dwell time of 1?h at 100?MPa yielded highly densified samples with the good transparency of 63 and 83% in visible and infra-red region, respectively. Optoceramics yielded a mechanical hardness of (3000 Hv)/ 29.42?GPa and a thermal conductivity of 21?Wm^?1?K^?1.     

Preliminary investigation of hydroxyapatite microstructures prepared by flash sintering

Flash sintering is a novel and emerging route for sintering ceramics within a few seconds, even under pressure-less conditions. In the current study, hydroxyapatite (HA) was fully densified by flash sintering at a furnace temperature of 1020°C. Flash sintering with constant electric fields of 750 and 1000?V?cm^?1 reduced the grain growth rate significantly compared to that sintered in the absence of an electric field at 1400°C. The microstructure of HA consolidated by flash sintering was compared with that of the without electric field sintered samples. The flash-sintered samples showed smaller grains (160?～?320?nm) than the without electric field sintered samples (～15?µm). The samples with a higher applied electric field showed slightly better densification than those with the lower field by flash sintering. Overall, the electric flash reduces the sintering temperature effectively and decreases the holding time to densify highly insulating ceramics, such as HA.     

Influence of processing conditions on the ionic conductivity of holmium zirconate (Ho2Zr2O7)

Nanopowders of holmium zirconate (Ho₂Zr₂O₇) synthesised through carbon neutral sol-gel method were pressed into pellets and individually sintered for 2 h in a single step sintering (SSS) process from 1100 °C to 1500 °C at 100 °C interval and in a two step sintering (TSS) process at (I) −1500 °C for 5 min followed by (II) - 1300 °C for 96 h. Relative density of each of the sintered pellet was determined using the Archimedes’ technique and the theoretical density was calculated from crystal structure data. Grain size was obtained from SEM micrographs using ImageJ. Pellets processed by TSS have been found to be denser (98 %) with less grain growth (1.29 μm) as compared to the pellets processed using SSS process. Ionic conductivity of Ho₂Zr₂O₇ pellets sintered by two different processes was measured using ac impedance spectroscopy technique over the temperature range of 350 °C–750 °C in the frequency range of 100 mHz–100 MHz for both heating and cooling cycles. The temperature dependence of bulk (2.67⨯10⁻³ Scm⁻¹) and grain boundary (2.50⨯10⁻³ Scm⁻¹) conductivities of Ho₂Zr₂O₇ prepared by TSS process are greater than those processed by SSS process suggesting the strong influence of processing conditions and grain size. Results of this study, indicates that the TSS is the preferable route for processing the holmium zirconate as it can be sintered to exceptionally high densities at lower temperature, exhibits less grain growth and enhanced ionic conductivity compared with the samples processed by SSS process. Hence, holmium zirconate can be considered as a promising new oxide ion conducting solid electrolyte for intermediate temperature SOFC applications between 350 °C and 750 °C temperature range.     

Development of a processing map for safe flash sintering of gadolinium-doped ceria

Flash sintering was discovered in 2010, where a dog-bone-shaped zirconia sample was sintered at a furnace temperature of 850°C in <5 s by applying electric fields of ~100 V cm⁻¹ directly to the specimen. Since its discovery, it has been successfully applied to several if not all oxides and even ceramics of complex compositions. Among several processing parameters in flash sintering, the electrical parameters, i.e., electric field and electric current, were found to influence the onset temperature for flash and the degree of densification respectively. In this work, we have systematically investigated the influence of the electrical parameters on the onset temperature, densification behavior, and microstructure of the flash sintered samples. In particular, we focus on the development of a processing map that delineates the safe and fail regions for flash sintering over a wide range of applied current densities and electric fields. As a proof of concept, gadolinium-doped ceria (GDC) is shown as an example for developing of such a processing map for flash sintering, which can also be transferred to different materials systems. Localization of current coupled with hot spot formation and crack formation is identified as two distinct failure modes in flash sintering. The grain size distribution across the current localized and nominal regions of the specimen was analyzed. The specimens show exaggerated grain growth near the positive electrode (anode). The region adjacent to the negative electrodes (cathode) showed retarded densification with large concentration of isolated pores. The electrical conductivity of the flash sintered and conventional sintered samples shows identical electrical conductivity. This quantitative analysis indicates that similar sintering quality of the GDC can be achieved by flash sintering at temperature as low as 680°C.     

Design of Electroceramics for Solid Oxides Fuel Cell Applications: Playing with Ceria

Nanostructured samaria- and gadolinia-doped ceria (SDC and GDC) powders were synthesized at low temperature (400°C) using diamine-assisted direct coprecipitation method. Fast-firing (f.f.) processes, where sintering temperatures are reached in a short time to promote lattice diffusion, were compared with conventional sintering, for the formation of dense microstructures from the nanostructured powders. Highly dense SDC and GDC samples (96%) with reduced grain size (150 nm) were obtained by f.f. even at 1300°–1400°C and, unexpectedly, high electrical conductivity and low blocking effect at grain boundary was obtained. Conventionally sintered samples showed that the grain boundary resistivity decreased with increasing the grain size, in agreement with the increase in geometrical bulk volume/grain boundary area ratio. Conversely, f.f. samples showed grain boundary resistivity smaller for small grain size. The above effect was observed only for high dopant (>10% molar) contents. The combined effect of powder grain size, dopant content, and sintering temperature–time profile, can be exploited to tune ceria microstructures for specific ionic device applications.     

Effect of Sm and Gd dopants on structural characteristics and ionic conductivity of ceria

Sm- and Gd-doped ceria electrolytes Ce_0.9Gd_0.1O_1.95 (GDC) and Ce_0.9Sm_0.1O_1.95 (SDC) were prepared by using the Pechini method. The microstructural and physical properties of the samples were characterized with X-ray diffraction (XRD), scanning electron microscopy (SEM), thermogravimetry/differential thermal analysis (TG/DTA) and Fourier Transform Infrared Spectroscopy (FTIR). The TG/DTA and XRD results indicated that a single-phase fluorite structure formed at a relatively low calcination temperature, 400 °C. The XRD patterns of the samples revealed that the crystallization of the SDC powders was superior than that of the GDC powders at 400 °C. The sintering behavior and ionic conductivity of the GDC and SDC pellets were also investigated. The sintering results showed that the SDC samples were found to have higher sinterability than the GDC samples at a relatively low sintering temperature, 1300 °C, a significantly lower temperature than 1650 °C, which is required for ceria solid electrolytes prepared by solid state techniques. The impedance spectroscopy results revealed that SDC has a higher ionic conductivity compared to GDC.     

Increased electrical conductivity and the mechanism of samarium‐doped ceria/Al2O3 nanocomposite electrolyte

To further enhance the electrical conductivity of doped ceria, the samarium‐doped ceria (SDC)/Al₂O₃ nanocomposites were prepared through sintering the coprecipitated powders in 1100°C‐1300°C. The grain sizes of all composites are less than 100 nm and decrease with alumina addition. Besides the main phases of SDC and Al₂O₃, the SmAlO₃ can precipitate in the composites if sintered at higher temperatures or for longer dwell time. The deviations of SDC diffraction peak positions demonstrate the solid solution of alumina into SDC lattice. The total electrical conductivities of the composites increase with alumina content until 30% alumina is added. The SDC/30%Al₂O₃ presents the higher total conductivity than the pure SDC by about five times. Specifically, the grain interior conductivity generally decreases with the alumina addition while the grain‐boundary conductivity increases with that. The introduction of the conductive SDC/Al₂O₃ interface can contribute to the rise of total conductivity, yet the excessive alumina addition also blocks the oxygen ion conduction. The SmAlO₃ precipitation is detrimental to the ion conduction for it consumes part of alumina and leads to the decrement in Sm concentration of SDC grain. Appropriate alumina addition not only enhances the conductivity of SDC but also lowers the material cost.     

High-Temperature Creep of Polycrystalline Magnesia: II,Effects of Additives *

The creep of magnesia doped with 0.035 to 2.26 cation % of nine other oxides and three binary mixtures thereof and of three seawater products (about 96, 98, and 99.5y0 MgO) was evaluated in transverse bending at 1200° to 1500°C, with strain rates of about 10−²%/hr, and average grain sizes of 5 to 50p. The results obtained were compared with those for pure magnesia. Most additives accentuated the plastic (diffusion-controlled) nature of the creep process presumably by pinning dislocations and/or slowing grain growth. In most cases the rate-determining diffusing species seemed to be the cation, Mg, but in two cases it was suspected that oxygen boundary diffusion was controlling. Porosities above ˜10% appear to increase the temperature dependence of creep, probably by introducing boundary sliding. The agreement of the creep data with those of other diffusion-controlled processes (electrical conductivity, sintering, and grain growth) is demonstrated.     

Ionic Transport Properties in Nanocrystalline Ce0.8A0.2O2-δ (with A = Eu,Gd, Dy,and Ho) Materials

The ionic transport properties of nanocrystalline 20 mol% Eu, Gd, Dy, and Ho doped cerias, with average grain size of around 14 nm were studied by correlating electrical, dielectric properties, and various dynamic parameters. Gd-doped nanocrystalline ceria shows higher value of conductivity (i.e., 1.8 × 10⁻⁴ S cm⁻¹ at 550°C) and a lower value of association energy of oxygen vacancies with trivalent dopants Gd³⁺ (i.e., 0.1 eV), compared to others. Mainly the lattice parameters and dielectric constants (ε_∞) are found to control the association energy of oxygen vacancies in these nanomaterials, which in turn resulted in the presence of grain and grain boundary conductivity in Gd- and Eu-doped cerias and only significant grain interior conductivity in Dy- and Ho-doped cerias.     

Temperature Dependence of Ionic Conductivity of Ceria Electrolyte at Concentrated Range of Multiple Doping

We study ionic conductivity of heavily doped ceria, doping level close to 50 mol% with multiple lanthanides in the temperature range of 200°C–500°C. The doped ceria is found to be single fluorite phase, where unit cell is dilated to 0.5527 nm, compared with pure ceria (0.5422 nm). Electrical characterization by impedance spectroscopy reveals that sample sintered at lower temperature (1400°C) has consistently higher bulk conductivity compared to sample sintered at higher (1600°C) temperature, throughout the temperature range studied. Activation energy for oxygen vacancy diffusion is close to 1 eV, indicating lesser association of defects with the dopants compared with other heavily doped ceria reported in literature (activation energy ~1.4 eV). The best ionic conductivity is found to be 1.58 × 10^?3 S/cm at 500°C, which is much higher compared with heavily doped ceria reported in literature.     

Influence of oxygen content on structure and properties of pressurelessly sintered aluminum-nitride- and zirconium-boride-doped silicon-carbide ceramics

SiC is a widely used material. Understanding how oxygen content affects the SiC structure and properties is crucial. In this paper, heat treatment was used to prepare SiC powder samples with different oxygen contents, which were doped with AlN and ZrB₂ and were densified by pressureless sintering at 2050 °C. The effect of oxygen content on the sintered SiC structure was determined by X-ray diffraction analysis, X-ray photoelectron spectroscopy, scanning electron microscopy, and energy-dispersive spectroscopy. The results indicated that the oxygen content influenced the SiC phase composition, grain boundaries, and densification. Additionally, the interaction between oxygen defects and AlN played an important role in sintering. The nanoindentation, alternating-current impedance, and thermal conductivity of the densified SiC specimens were also evaluated to elucidate the influence of the oxygen content on the densified-SiC functional properties. The results revealed that the oxygen content affected all the measured mechanical, electrical, and thermal properties. Furthermore, surface oxygen impurities suggested that oxygen content had similar critical effects on both the densified SiC structure and properties.     

Electrically conductive SiC ceramics processed by pressureless sintering

Polycrystalline SiC ceramics with 10 vol% Y₂O₃-AlN additives were sintered without any applied pressure at temperatures of 1900-2050°C in nitrogen. The electrical resistivity of the resulting SiC ceramics decreased from 6.5 × 10¹ to 1.9 × 10⁻² Ω·cm as the sintering temperature increased from 1900 to 2050°C. The average grain size increased from 0.68 to 2.34 μm with increase in sintering temperature. A decrease in the electrical resistivity with increasing sintering temperature was attributed to the grain-growth-induced N-doping in the SiC grains, which is supported by the enhanced carrier density. The electrical conductivity of the SiC ceramic sintered at 2050°C was ~53 Ω⁻¹·cm⁻¹ at room temperature. This ceramic achieved the highest electrical conductivity among pressureless liquid-phase sintered SiC ceramics.     

Improved microstructure and sintering temperature of bismuth nano-doped GDC powders synthesized by direct sol-gel combustion

To improve the microstructural and electrochemical properties of Gadolinium-doped ceria (GDC) electrolytes, materials co-doped ceria with bismuth oxide (1–5 mol%) have been successfully prepared in a one-step sol-gel combustion synthetic route. Sol-gel combustion facilitates molecular mixing of the precursors and substitution of the large Bi³⁺ cations into the fluorite structure, considerably reducing the sintering temperature. Adding Bi₂O₃ as a dopant increases the GDC densification to above 99.7% and reduces its traditional sintering temperature by 300 °C. Impedance analyses show that the addition of bismuth enhances the conductivity (3.1?10^?2?1.7?10^?1 S·cm^?1 in the temperature range 600–800 °C) and improves the performance of the solid electrolyte in intermediate-temperature solid oxide fuel cells.