Multiscale modeling of the ionic conductivity of acceptor doped ceria

The ionic conductivity of acceptor doped ceria is strongly influenced by grain boundaries and interfaces, with most experiments showing a conductivity decrease in these regions. Classical models explain this observation by the formation of space charge layers, that are depleted of mobile ionic charge carriers. However, some experiments demonstrate an increase in ionic conductivity and recent models show that the space charge layers can also be enriched in mobile ionic species. Because of these discrepancies, it is still not certain whether nanocrystalline or thin film ceria can offer superior ionic conductivity or not. Recently, we have demonstrated by means of Monte Carlo simulations that the ionic conductivity in space charge layers can indeed exceed the bulk value. In this work, we combine these Monte Carlo simulations with a continuum model to predict charge carrier concentration profiles. This multiscale approach allows for a realistic prediction of the grain boundary ionic conductivity.     

The ionic conductivity of Sm-doped ceria

The oxygen ion conductivity of polycrystalline samples of Sm-doped ceria and of Gd-doped ceria is studied as a function of doping fraction and temperature using impedance spectroscopy allowing the separation of bulk and grain boundary conductivity. The introduction of a fine spacing for the Sm dopant fraction allows the clear identification of the dopant fraction leading to the largest bulk conductivity. At 267°C, the largest bulk conductivity is shown for Ce_0.93Sm_0.07O_1.965. With increasing temperature, indications of an increase in the dopant fraction, which leads to the maximum in conductivity, are found. For the grain boundary conductivity, the maximum appears at larger dopant fractions compared to the bulk conductivity. The largest total conductivity for both dopants is again found for Sm-doped ceria. In literature, different syntheses and sample preparation methods led to larger total conductivities for Gd-doped ceria. In this work, we demonstrate that the variation of sintering conditions leads to scattering in the conductivity over one order of magnitude. Finally, we demonstrate that, in nominally pure cerium oxide, impurities dominate the ionic conductivity.     

Electrochemical and thermal characterization of doped ceria electrolyte with lanthanum and zirconium

Nanocomposites electrolytes consisting of La³⁺ and Zr⁴⁺ doped with ceria labelled as La_0.2 Ce_0.8 O_2-δ (LDC), Zr_0.2Ce_0.8O_2-δ (ZDC) and Zr_0.2La_0.2Ce_0.6O_2-δ (ZLDC) have been synthesized via a co-precipitation route. DC conductivity was studied with a four-probe method in the range of temperature 450–650 °C and maximum conductivity was found to be 0.81 × 10^?2 S.cm^?1 (LDC) > 0.32 × 10^?2 S.cm^?1 (ZLDC) > 0.15 × 10^?2 S.cm^?1 (ZDC) at a temperature of 650 °C, respectively. Further, electric behavior of doped and co-doped ceria electrolytes was investigated by A.C electrochemical impedance spectroscopy (frequency range ~ 0.1 Hz?4 MHz). The phase/structural identification of the material prepared was studied using X-ray diffraction and found ceria to possess a cubic fluorite structure. Scanning electron microscopy (SEM) was carried out to study its morphology and particle size (~ 90–120 nm). Thermal behavior on its change in weight and length with the temperature were studied by thermogravimetric analysis (TGA) and dilatometry respectively. Furthermore, thermal expansion coefficients (TECs) of prepared electrolytes are calculated and found as follows: 13.4 × 10^?6 °C^?1, 13.6 × 10^?6 °C^?1and 15.3 × 10^?6 °C^?1 for LDC, ZDC and ZLDC, respectively, in the temperature range 150–1150 °C.     

Electrical properties of samaria-doped ceria electrolytes from highly active powders

The correlations of the microstructures and the electrical properties of high reactive Ce_0.8Sm_0.2O_1.9 (SDC) powders, synthesized via an optimal carbonate coprecipitation method, were investigated. Microstructure of the SDC ceramics sintered at 900-1400 °C showed uniform grain and small grain size, compared with those prepared with various methods under similar sintering conditions. These features may be related to high conductivity (σ_600 °C = 0.022 S cm⁻¹) and low activation energy for conduction (0.66 eV). AC impedance spectra were involved to resolve grain interior and grain boundary resistance. Grain boundary contribution to the total resistance showed the values below 1/2 at 200-450 °C, suggesting low grain boundary effect. The motion enthalpy for the grain interior conduction decreased while the association enthalpy increased with sintering temperature up to 1300 °C, which might be possibly originated from the increase in lattice parameters with the sintering temperature.     

Ionic conductivity of space charge layers in acceptor doped ceria

The ionic conductivity of acceptor doped ceria is strongly influenced by grain boundaries and interfaces. Most experiments show a decrease in ionic conductivity and an increase in electronic conductivity in these regions. Classical models explain this observation by the formation of space charge layers that are depleted of mobile ionic charge carriers and enriched in small polarons. However, some experiments demonstrate an increase in ionic conductivity and recent models show that the space charge layers can also be enriched in mobile ionic species. Because of these contradictions, it is still not clear whether nanocrystalline or thin film ceria can offer superior ionic conductivity or not. To aid this debate, we calculate the ionic conductivity of yttrium doped ceria in regions of net charge density using kinetic Monte Carlo simulations. Through an appropriate choice of the charge densities, these calculations allow to demarcate the possible conductivity gains from space charge layers.     

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.     

Effect of divalent cation addition on structure,conductivity and grain boundary properties in La doped ceria oxygen ion conductors

The aim of this work is to investigate the effect of divalent cations on the structure and electrical properties of Ce_0.85La_0.1D_0.05O_2-δ (D = Ca, Sr and Ba) oxygen ion conductors. The X-Ray structural analysis confirms the presence of CeDO₃ minor phase in addition to cubic fluorite phase of ceria in Sr²⁺ and Ba²⁺ added compositions. The lattice parameter of the compositions significantly depends on the ionic radius of dopants and the presence of D²⁺ ions in ceria lattice. The Ca²⁺ added composition shows the highest free oxygen vacancy concentration due to its lowest association energy and complete dissolution of Ca²⁺ ions into ceria lattice. The dopant-vacancy association energy and grain interior conductivity changes with the ionic radii of the divalent dopants. The grain boundary capacitance depends on dielectric constant, grain size and grain boundary thickness. The grain boundary conductivity shows 46% over total conductivity for Sr²⁺ added composition. The presence of CeDO₃ phase and space charge layer promotes the grain boundary resistances and affects the ion dynamics. Schematic models are proposed to understand the ion migration in grain boundaries. The scavenging effect is found to be highest in Sr²⁺ ions added composition. The defect structures, the presence of CeDO3 phase and electrical properties are correlated with each other.     

Improved ionic conductivity of nitrile rubber/ionic liquid composites

Polymer electrolytes with high ionic conductivity and good elasticity were prepared by mixing nitrile rubber (poly(acrylonitrile-co-butadiene) rubber; NBR) with ionic liquid, N-ethylimidazolium bis(trifluoromethanesulfonyl)imide (EImTFSI). The NBR/EImTFSI composites were obtained as homogeneous and transparent films when the ionic liquid content was less than 60 wt%. Raman spectroscopy suggested the interaction between nitrile group of NBR and TFSI anion. Sample with ionic liquid content of 50 wt% showed the ionic conductivity of 1.2×10⁻⁵ S cm⁻¹ at 30 °C. Addition of lithium salt to this NBR/EImTFSI composite further enhanced the ionic conductivity to about 10⁻⁴ S cm⁻¹ without spoiling mechanical properties. DSC studies showed two glass transition temperatures for composites indicating microphase separation.     

Samarium doped ceria (SDC) synthesized by a metal triethanolamine complex decomposition method: Characterization and an ionic conductivity study

Samarium doped ceria (SDC) powders as solid electrolyte ceramics were successfully prepared via thermal decomposition of metal organic complexes containing triethanolamine (TEA) as a ligand. The SDC powders synthesized using various samarium doping contents were characterized by X-ray diffractometry, scanning electron microscopy, X-ray absorption spectroscopy, energy dispersive X-ray spectroscopy and Brunauer-Emmett-Teller (BET) analysis. The influences of samarium doping and the calcination temperature on the characteristics of the SDC materials were thoroughly investigated. An appropriate temperature for SDC powder calcination was identified by thermogravimetric analysis to be 600 °C. After sintering the calcined SDC powders at 1500 °C to obtain highly dense ceramic pellets, the electrical conductivity of the materials was examined by impedance spectroscopy. The influence of percentage of Sm³⁺ dopants in SDC materials on the observed conductivity were explained by correlating with the detailed analysis of the local structure and environment of Sm³⁺ within the SDC materials by using X-ray absorption spectroscopy. The conductivities of the SDC products reported in this work indicate that they are promising candidates for solid electrolytes in solid oxide fuel cell applications.     

Grain boundary conductivity of Ce0.8Ln0.2O2−δ ceramics (Ln = Y, La, Gd, Sm) with and without Co-doping

The acetylacetone precursor method was used to obtain powders of different ceria-based Ce_0.8Ln_0.2O_2−δ (Ln = Y, Gd, Sm, La) compositions, and these powders were used to prepare disks which were sintered at 1150 °C after addition of Co nitrate, or at 1500 °C, without Co. These materials were characterized by impedance spectroscopy to distinguish the bulk and grain boundary behaviours. Arrhenius representations of bulk conductivity data show a gradual slope change, indicating defect interactions on cooling to intermediate and relatively low temperatures. Though data for different doped-ceria samples converge in the high temperature range, significant differences in conductivity and activation energy were found at low temperatures. The grain boundary behaviour shows dependence on the trivalent additive (Y, La, Gd or Sm), and the highest grain boundary conductivity for samples obtained without addition of cobalt nitrate was found for samples with La. However, addition of cobalt nitrate and sintering at relatively low temperature enhances the grain boundary conductivity of the remaining materials. The highest specific grain boundary conductivity was then found for samples containing Sm. Differences in grain boundary behaviour were interpreted based on differences in segregation of the rare earth additives for samples without Co-doping and preferential segregation of Co for Co-doped samples.     

Impedance spectroscopy modeling of lithium borate with silica: A dispersed ionic conductor system

Lithium borate/silica composites, 40 wt% SiO₂ with x·Li₂O+(1-x)·B₂O₃, x=0.33, 0.50, were explored with the goal of achieving Li-ion conductivity enhancements across batches with different compositions and processing steps. Two batches were made for each composition, namely micron and nanoscale batches, which differ in their processing and fabrication methods. Phase and microstructural characterization showed a composite which is consisted of a conductor-rich and an insulator-rich region. Previous dispersed ionic conductors, in which conductivity is enhanced by the insulator/conductor interaction, were modeled mostly by percolation models. However, these percolation models are not compatible with conventional impedance spectroscopy circuit models and complex non-linear regression analysis. Hence, new circuit models were created based upon a brick-layer construction that assumed dispersed ionic conductor phenomena to be present. The new circuit models, which are named the theoretical model (TM) and approximation model (AM), uniquely and accurately fitted the impedance spectroscopy data and correctly showed lower resistance and activation energy values for the interfacial conduction pathways. Meanwhile, a typical circuit model which has two parallel RC circuits (2P) showed an anomalous high-frequency M” tail in some samples which does not correspond to the expectations of a realistic and physical modulus data. The combined activation energy and interface activation energy from the new models were compared to literature values of lithium borate conductors and Li-ion dispersed ionic conductors. The comparison results suggested that conductivity of the lithium borate/silica composites can be further enhanced through compositional, microstructural, and phase control.     

Influence of rare earth additives and boron component on electrical conductivity of sodium rare earth borate glasses

Sodium rare earth borate glasses (Na₂O)_35.7(RE₂O₃)_7.2(B₂O₃)_57.1 (RE = Sm, Gd, Dy, Ho, Y, Er, and Yb), were prepared from a mixture of Na₂CO₃, RE₂O₃ and B₂O₃, and their properties as an Na⁺ ionic conductor were investigated. Density increased with increasing atomic weight of RE. Crystallization temperature and crystal melting temperature of the present borate system was lower than that of the previously reported silicate and germanate system. Results of the ¹¹B NMR measurement suggested that half of all boron atoms are coordinated by four oxide ions to give a [BO₄] tetrahedral unit and the others are coordinated by three oxide ions to give a [BO₃] planar triangular unit. The electrical conductivity slightly decreased with increasing the ionic radius of RE³⁺. (Na₂O)_35.7(Y₂O₃)_7.2(B₂O₃)_57.1 glass exhibited the electrical conductivity which is about one order of magnitude lower than those of the previously reported (Na₂O)_35.7(Y₂O₃)_7.2(SiO₂)_57.1 and (Na₂O)_35.7(Y₂O₃)_7.2(GeO₂)_57.1 glasses. It was assumed that this lower electrical conductivity is due to the lower content of Na⁺ ions as conduction species in the former glass, compared with the latter two glasses.     

Ionic conductivity in Bi2Sn2O7 ceramics

Impedance spectroscopy measurements, in the temperature range from room temperature to 600 K, were performed in order to investigate the dielectric and ionic properties of Bi₂Sn₂O₇ ceramics. The results show that the conductivity in this pyrochlore is associated with the hopping of ions. An activation energy of 1.26 eV was observed and the dielectric constant exhibits a strong contribution from ionic conduction.     

Enhanced ionic conductivity of scandia-ceria-stabilized-zirconia (10Sc1CeSZ) electrolyte synthesized by the microwave-assisted glycine nitrate process

Scandia-stabilized-zirconia is a potential zirconia-based electrolyte for intermediate temperature solid oxide fuel cells (IT-SOFCs). In this study, the properties of zirconia co-doped with 10 mol% Sc and 1 mol% Ce (scandia-ceria-stabilized-zirconia, 10Sc1CeSZ) electrolyte synthesized by the microwave-assisted glycine nitrate process (MW-GNP) were determined. The effects of microwave heating on the sintering temperature, microstructure, densification and ionic conductivity of the 10Sc1CeSZ electrolyte were evaluated. The phase identification, microstructure and specific surface area of the prepared powder were investigated using X-ray diffraction, transmission electron microscopy and the Brunauer-Emmett-Teller technique, respectively. Using microwave heating, a single cubic-phase powder was produced with nanosized crystallites (19.2 nm) and a high specific surface area (16 m²/g). It was found that the relative density, porosity and total ionic conductivity of the 10Sc1CeSZ electrolyte are remarkably influenced by the powder processing method and the sintering temperature. The pellet sintered at 1400 °C exhibited a maximum ionic conductivity of 0.184 S/cm at 800 °C. This is the highest conductivity value of a scandia-stabilized-zirconia based electrolyte reported in the literature for this electrolyte type. The corresponding value of the activation energy of electrical conductivity was found to be 0.94 eV in the temperature range of 500–800 °C. Overall, the use of microwave heating has successfully improved the properties of the 10Sc1CeSZ electrolyte for application in an IT-SOFC.     

Studies on ionic conductivity of stabilized zirconia ceramics (8YSZ) densified through conventional and non-conventional sintering methodologies

Densification studies of 8 mol% yttria stabilized zirconia ceramics were carried out by employing the sintering techniques of conventional ramp and hold (CRH), spark plasma sintering (SPS), microwave sintering (MWS) and two-stage sintering (TSS). Sintering parameters were optimized for the above techniques to achieve a sintered density of >99% TD. Microstructure evaluation and grain size analysis indicated substantial variation in grain sizes, ranging from 4.67 μm to 1.16 μm, based on the sintering methodologies employed. Further, sample was also sintered by SPS technique at 1425 °C and grains were intentionally grown to 8.8 μm in order to elucidate the effect of grain size on the ionic conductivity. Impedance spectroscopy was used to determine the grain and grain boundary conductivities of the above specimens in the temperature range of RT to 800 °C. Highest conductivity of 0.134 S/cm was exhibited by SPS sample having an average grain size of 1.16 μm and a decrease in conductivity to 0.104 S/cm was observed for SPS sample with a grain size of 8.8 μm. Ionic conductivity of all other samples sintered vide the techniques of TSS, CRH and MWS samples was found to be ∼0.09 S/cm. Highest conductivity irrespective of the grain size of SPS sintered samples, can be attributed to the low densification temperature of 1325 °C as compared to other sintering techniques which necessitated high temperatures of ∼1500 °C. The exposure to high temperatures while sintering with TSS, CRH and MWS resulted into yttria segregation leading to the depletion of yttria content in fully stabilized zirconia stoichiometry as evidenced by Energy Dispersive Spectroscopy (EDS) studies.     

Toward nanograined gadolinia doped ceria via two-step sintering at ultralow temperature and its electrical conductivity

Highly dense (>98%) and nanograined (∼60 nm) gadolinia doped ceria are obtained from ultrafine powders by adopting two-step sintering (TSS) procedure at an ultralow temperature of 750 °C with a dwell time of 20 h, which is the lowest sintering temperature for ceria family without sintering aids up to now. Electrochemical impedance spectroscopy investigations suggest that the electrical conductivities of densified electrolytes are closely related to sintering temperature and grain size, and GDC900-750 exhibits the highest total electrical conductivity of 3.640 S m⁻¹ at 700 °C in air. Fitting calculation indicates partial grain-size dependence of oxygen vacancy association enthalpy and grain-size independence of oxygen ion migration enthalpy. Grain boundary maturity influences on grain boundary conductivity to some extent, and younger grain boundary endues the densified electrolytes with higher grain boundary conductivity.     

Adsorption and desorption characteristics of arsenic onto ceria nanoparticles

The rapid increase in the use of engineered nanoparticles [ENPs] has resulted in an increasing concern over the potential impacts of ENPs on the environmental and human health. ENPs tend to adsorb a large variety of toxic chemicals when they are emitted into the environment, which may enhance the toxicity of ENPs and/or adsorbed chemicals. The study was aimed to investigate the adsorption and desorption behaviors of arsenic on ceria NPs in aqueous solution using batch technique. Results show that the adsorption behavior of arsenic on ceria NPs was strongly dependent on pH and independent of ionic strength, indicating that the electrostatic effect on the adsorption of these elements was relatively not important compared to surface chemical reactions. The adsorption isotherms fitted very well to both the Langmuir and Freundlich models. The thermodynamic parameters (ΔH ⁰ , ΔS ⁰ , and ΔG ⁰ ) for the adsorption of arsenic were determined at three different temperatures of 283, 303, and 323 K. The adsorption reaction was endothermic, and the process of adsorption was favored at high temperature. The desorption data showed that desorption hysteresis occurred at the initial concentration studied. High adsorption capacity of arsenic on ceria NPs suggests that the synergistic effects of ceria NPs and arsenic on the environmental systems may exist when they are released into the environment.     

Re-examination of bulk and grain boundary conductivities of Ce1−xGdxO2−δ ceramics

Powders of gadolinium-doped ceria solid solutions, Ce_1−xGd_xO_2−δ (x = 0.05, 0.1, 0.2, 0.3 and 0.4), were prepared by a freeze-drying precursor route. Dense ceramic pellets with average grain sizes in the range of several microns were obtained after sintering at 1600 °C. Cobalt nitrate was added to the powders to obtain dense ceramic samples with grain sizes in the submicrometer range at 1150 °C. The ionic conduction was analysed by impedance spectroscopy in air, to de-convolute the bulk and grain boundary contributions. The bulk conductivity at low temperature clearly decreases with increasing content of Gd whereas the activation energy increases. An alternative method is proposed to analyse the extent of defect interactions on conduction. For samples without addition of Co, the specific grain boundary conductivity increases with increasing Gd content. Addition of cobalt does not alter the bulk properties but produces an important increase in the specific grain boundary conductivity, mainly in samples with lower Gd-concentration (x = 0.05 and 0.1). Segregation of Gd and its strong interaction with charge carriers may explain the blocking effects of grain boundaries.     

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.