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Mixed ionic and electronic conducting (MIEC) materials recently gained much interest for use as anodes in solid oxide fuel cell (SOFC) applications. However, many processes in MIEC-based porous anodes are still poorly understood and the appropriate interpretation of corresponding electrochemical impedance spectroscopy (EIS) data is challenging. Therefore, a model which is capable to capture all relevant physico-chemical processes is a crucial prerequisite for systematic materials optimization. In this contribution we present a comprehensive model for MIEC-based anodes providing both the DC-behaviour and the EIS-spectra. The model enables one to distinguish between the impact of the chemical capacitance, the reaction resistance, the gas impedance and the charge transport resistance on the EIS-spectrum and therewith allows its appropriate interpretation for button cell conditions. Typical MIEC-features are studied with the model applied to gadolinium doped ceria (CGO) anodes with different microstructures. The results obtained for CGO anodes reveal the spatial distribution of the reaction zone and associated transport distances for the charge carriers and gas species. Moreover, parameter spaces for transport limited and surface reaction limited situations are depicted. By linking bulk material properties, microstructure effects and the cell design with the cell performance, we present a way towards a systematic materials optimization for MIEC-based anodes. [ABSTRACT FROM AUTHOR]

The degradation of sputtered columnar ZnO layers under DC polarization was studied by using electrochemical impedance spectroscopy and electron microscopy. It was found that the structure of the as‐deposited ZnO film was dense at the nanoscale. An equivalent circuit model including de Levie impedance accounted for the localized propagation of microscale cracks towards the copper substrate. This generates a capacitance (CZnO) that represents the crack surface area in contact with the electrolyte. CZnO is small enough not to be obscured by the double layer capacitance at the top of the layers and increases with increasingly negative potential and time. These results were compared to nanoporous ZnO layers that behave differently and exhibit a large CZnO. The combination of in situ EIS analysis with the ex situ structural information provided by electron microscopy proved to be an efficient methodology to characterize very different microstructures of conductive coatings. [ABSTRACT FROM AUTHOR]

Zinc oxide (ZnO) films with nano‐granular structure were deposited by radio‐frequency magnetron sputtering. The absence of preferred orientation was verified by XRD. HAADF‐STEM images revealed a nanoporous structure with pore and grain sizes around 10 nm. The narrowness of the pores enabled to approximate that oxygen reduction takes place at the surface of the layers. During cathodic polarization, the surface of the electrodes became rougher due to the development of nodules on the surface. The ZnO electrodes exhibit a high activity towards oxygen reduction in KOH solution (pH=10). Rotating ring‐disk electrode measurements coupled with reaction modelling allowed to quantitatively demonstrate that the direct reduction prevailed with the indirect pathway being active as well. [ABSTRACT FROM AUTHOR]

Abstract: Zinc electrodes were polarized cathodically at moderate overpotentials in NaCl 0.6 M solutions under potentiostatic conditions for 7 to 17 hours at room temperature. Corrosion products were characterized by using optical microscopy, XRD, Raman microscopy, XPS, and FIB‐SEM. Close to the open‐circuit potential, the corrosion products were formed by simonkolleite and the electrochemical response exhibits anodic features. At more negative potentials, the current density remains cathodic throughout the polarization and the deposits on the electrode surface consist almost solely of ZnO. The soluble zinc species necessary for ZnO deposition originate from localized dissolution of the substrate in the form of pits. This effect is assigned to the strong alkalinization of the surface due to oxygen reduction. Despite developing greater surface area than bare zinc substrates, the nanostructured ZnO deposits reduced the cathodic activity. [ABSTRACT FROM AUTHOR]

The analysis of big data is changing industries, businesses and research as large amounts of data are available nowadays. In the area of microstructures, acquisition of (3-D tomographic image) data is difficult and time-consuming. It is shown that large amounts of data representing the geometry of virtual, but realistic 3-D microstructures can be generated using stochastic microstructure modeling. Combining the model output with physical simulations and data mining techniques, microstructure-property relationships can be quantitatively characterized. Exemplarily, we aim to predict effective conductivities given the microstructure characteristics volume fraction, mean geodesic tortuosity, and constrictivity. Therefore, we analyze 8119 microstructures generated by two different stochastic 3-D microstructure models. This is-to the best of our knowledge-by far the largest set of microstructures that has ever been analyzed. Fitting artificial neural networks, random forests and classical equations, the prediction of effective conductivities based on geometric microstructure characteristics is possible. © 2017 American Institute of Chemical Engineers AIChE J, 63: 4224-4232, 2017 [ABSTRACT FROM AUTHOR]

Perovskite-type oxides have shown the ability to reversibly segregate precious metals from their structure. This reversible segregation behavior was explored for a commonly used catalyst metal, Ni, to prevent Ni sintering, which is observed on most catalyst support materials. Temperature-programmed reduction, X-ray diffraction, X-ray absorption spectroscopy, electron microscopy, and catalytic activity tests were used to follow the extent of reversible Ni segregation. LaFe1− xNi xO3± δ (0≤ x≤0.2) was synthesized using a citrate-based solution process. After reduction at 600 °C, metallic Ni particles were displayed on the perovskite surfaces, which were active towards the hydrogenation of CO2. The overall Ni reducibility was proportional to the Ni content and increased from 35 % for x=0.05 to 50 % for x=0.2. Furthermore, Ni could be reincorporated reversibly into the perovskite lattice during reoxidation at 650 °C. This could be exploited for catalyst regeneration under conditions under which impregnated materials such as Ni/LaFeO3± δ and Ni/Al2O3 suffer from sintering. [ABSTRACT FROM AUTHOR]

This paper presents a proof-of-concept study and demonstrates the next generation of a “smart” catalyst material, applicable to high temperature catalysis and electro-catalysis such as gas processing and as a catalyst for solid oxide cells. A modified citrate-gel technique was developed for the synthesis of LaxSr1−1.5xTi1−yNiyO3−δ. This method allowed the synthesis of single phase materials with a high specific surface area, after the first calcination step at temperatures as low as 650 °C. Up to 5 at% of nickel could be incorporated into the perovskite structure at this low calcination temperature. X-ray powder diffraction and microscopy techniques have proven the exsolution of nickel nanoclusters under low oxygen partial pressure. The amount of exsoluted nickel nanoparticles was sensitive to surface finishing, whereby much more exsoluted nanoparticles were observed on pre-treated and polished surfaces as compared to original ones. Increasing A-site deficiency leads to a larger number of nickel particles on the surface, indicating a destabilizing influence of the A-site vacancies on the B-site metal cations. Repetitive redox cycles prove that the nickel exsolution and re-integration is a fully reversible process. These materials working in a cyclic and repetitive way may overcome the drawbacks of currently used conventional catalysts used for high temperature systems and overcome major degradation issues related to catalyst poisoning and coarsening-induced aging. [ABSTRACT FROM AUTHOR]

Empirical relationships between effective conductivities in porous and composite materials and their geometric characteristics such as volume fraction [ABSTRACT FROM AUTHOR]

3D microstructure-performance relationships in Ni-YSZ anodes for electrolyte-supported cells are investigated in terms of the correlation between the triple phase boundary (TPB) length and polarization resistance (Rpol). Three different Ni-YSZ anodes of varying microstructure are subjected to eight reduction-oxidation (redox) cycles at 950 °C. In general the TPB lengths correlate with anode performance. However, the quantitative results also show that there is no simplistic relationship between TPB and Rpol. The degradation mechanism strongly depends on the initial microstructure. Finer microstructures exhibit lower degradation rates of TPB and Rpol. In fine microstructures, TPB loss is found to be due to Ni coarsening, while in coarse microstructures reduction of active TPB results mainly from loss of YSZ percolation. The latter is attributed to weak bottlenecks associated with lower sintering activity of the coarse YSZ. The coarse anode suffers from complete loss of YSZ connectivity and associated drop of TPBactive by 93%. Surprisingly, this severe microstructure degradation did not lead to electrochemical failure. Mechanistic scenarios are discussed for different anode microstructures. These scenarios are based on a model for coupled charge transfer and transport, which allows using TPB and effective properties as input. The mechanistic scenarios describe the microstructure influence on current distributions, which explains the observed complex relationship between TPB lengths and anode performances. The observed loss of YSZ percolation in the coarse anode is not detrimental because the electrochemical activity is concentrated in a narrow active layer. The anode performance can be predicted reliably if the volume-averaged properties (TPBactive, effective ionic conductivity) are corrected for the so-called short-range effect, which is particularly important in cases with a narrow active layer. [ABSTRACT FROM AUTHOR]

This study investigates the influence of microstructure on the effective ionic and electrical conductivities of Ni-YSZ (yttria-stabilized zirconia) anodes. Fine, medium, and coarse microstructures are exposed to redox cycling at 950 °C. FIB (focused ion beam)-tomography and image analysis are used to quantify the effective (connected) volume fraction (Φeff), constriction factor (β), and tortuosity (τ). The effective conductivity (σeff) is described as the product of intrinsic conductivity (σ0) and the so-called microstructure-factor (M): σeff = σ0 × M. Two different methods are used to evaluate the M-factor: (1) by prediction using a recently established relationship, Mpred = εβ0.36/τ5.17, and (2) by numerical simulation that provides conductivity, from which the simulated M-factor can be deduced (Msim). Both methods give complementary and consistent information about the effective transport properties and the redox degradation mechanism. The initial microstructure has a strong influence on effective conductivities and their degradation. Finer anodes have higher initial conductivities but undergo more intensive Ni coarsening. Coarser anodes have a more stable Ni phase but exhibit lower YSZ stability due to lower sintering activity. Consequently, in order to improve redox stability, it is proposed to use mixtures of fine and coarse powders in different proportions for functional anode and current collector layers. [ABSTRACT FROM AUTHOR]

Nanoporous 1-μm thin La 0.6 Sr 0.4 CoO 3− δ (LSC) layers are deposited by spray pyrolysis and subsequently sintered at 600 °C, 800 °C, and 1000 °C. A strontium- and oxygen-rich phase can be found within the pore network, which appears at low sintering temperatures. This so-called “secondary phase” occupies up to 20.7 vol.% of the LSC films for the 600 °C annealing process. It does not hinder the electrochemical activity towards oxygen reduction of such layers that exhibit an area-specific resistance (ASR) as low as 0.13 Ω cm 2 at 600 °C in air. This result makes the spray pyrolysed LSC thin films promising candidates as intermediate-temperature solid oxide fuel cell cathodes. For higher sintering temperatures the secondary phase progressively disappears. A correlation between the inverse of the ASR and the whole LSC surface area (regardless of the presence of the secondary phase or not) is also evidenced. The increase of ASR with increasing sintering temperature is found to be primarily related to the exchange neutral flux density of the Sr-deficient LSC. [ABSTRACT FROM AUTHOR]

The microstructure influence on conductive transport processes is described in terms of volume fraction ε, tortuosity τ, and constrictivity β. Virtual microstructures with different parameter constellations are produced using methods from stochastic geometry. Effective conductivities [ABSTRACT FROM AUTHOR]

The ion conductivity of two series of porous ceramic diaphragms impregnated with caustic potash was investigated by electrochemical impedance spectroscopy. To understand the impact of the pore structure on ion conductivity, the three-dimensional (3-D) pore geometry of the diaphragms was characterized with synchrotron x-ray absorption tomography. Ion migration was calculated based on an extended pore structure model, which includes the electrolyte conductivity and geometric pore parameters, for example, tortuosity (τ) and constriction factor (β), but no fitting parameters. The calculated ion conductivities are in agreement with the data obtained from electrochemical measurements on the diaphragms. The geometric tortuosity was found to be nearly independent of porosity. Pore path constrictions diminish with increasing porosity. The lower constrictivity provides more pore space that can effectively be used for mass transport. Direct measurements from tomographs of tortuosity and constrictivity opens new possibilities to study pore structures and transport properties of porous materials. [ABSTRACT FROM AUTHOR]

Portland cement powder, ground from much larger clinker particles, has a particle size distribution from about 0.1 to 100 μm. An important question is then: does particle shape depend on particle size? For the same cement, X-ray computed tomography has been used to examine the 3-D shape of particles in the 20–60 μm sieve range, and focused ion beam nanotomography has been used to examine the 3-D shape of cement particles found in the 0.4–2.0 μm sieve range. By comparing various kinds of computed particle shape data for each size class, the conclusion is made that, within experimental uncertainty, both size classes are prolate, but the smaller size class particles, 0.4–2.0 μm, tend to be somewhat more prolate than the 20–60 μm size class. The practical effect of this shape difference on the set-point was assessed using the Virtual Cement and Concrete Testing Laboratory to simulate the hydration of five cement powders. Results indicate that nonspherical aspect ratio is more important in determining the set-point than are the actual shape details. [ABSTRACT FROM AUTHOR]

Focused ion beam nanotomography (FIB-nt) is a novel method for high resolution three-dimensional (3D) imaging. In this investigation we assess the methodological parameters related to image acquisition and data processing that are critical for obtaining reproducible microstructural results from granular materials and from complex suspensions. For this purpose three case studies are performed: (1) The precision of FIB-nt is evaluated by analyzing a reference sample with nanospheres. Due to the implementation of an automated correction procedure, drift phenomena can be removed largely from the FIB data. However, at high magnifications remaining drift components can induce problems for 3D-shape reconstructions. (2) Correct object recognition from densely packed microstructures requires specific algorithms for splitting of agglomerated particles. To establish quantitative criteria for the correct degree of splitting, a parametric study with dry portland cement is performed. It is shown that splitting with a k-value of 0.6 leads to accurate results. (3) Finally, the reproducibility of the entire cryo-FIB analysis is investigated for high pressure frozen cement suspensions. Reproducible analyses can be obtained if the magnification is adapted to the particle size. At low magnifications the small particles and their surface area are underestimated. At high magnifications representativity is questioned because local inhomogeneities can become dominant. [ABSTRACT FROM AUTHOR]

FIB-nanotomography (FIB-nt) is applied to record high-resolution 3D pore networks from cementitious materials. Based on these data, it is examined as to why the pore size distribution (PSD), which is obtained from traditional analysis by mercury intrusion porosimetry (MIP), principally deviates from the findings that are achieved by common back-scattered electron image analysis. The paper does not reflect the vulnerability of the physical model assumptions, but merely focuses on the fundamental issues of the geometrical definition of a PSD. A computationally fast approach for the PSD assessment from 3D data as well as for the simulation of MIP is presented and the varying concepts for the definition of a PSD are compared with each other. [ABSTRACT FROM AUTHOR]

A new 3D-microscopy method, focused ion beam-nanotomography (FIB-nt), has been applied to the statistical particle shape analysis and for topological characterization of granular textures in cement samples. Because of its high resolution (15 nm), FIB-nt reveals precise microstructural information at the submicrometer scale, which cannot be obtained with conventional tomography methods. It is demonstrated that even from complex granular textures with dense agglomerates, it is possible to identify the individual sub-grains. This is the basis for reliable statistical shape analysis. For this purpose, moments of inertia were determined for particles from five different grain size fractions of a given cement, which provides important input data for future modeling of rheology and hydration processes. In addition, FIB-nt was used for topological characterization of the particle–particle interfaces in the dense and fine-grained granular textures. The unique 3D-data obtained with FIB-nt thus open new possibilities for quantitative microstructure analysis and the data can be used as structural input for object-oriented modeling. [ABSTRACT FROM AUTHOR]

The focused ion beam-nanotomography (FIB-nt) technique presented in Part I of this article is a novel high-resolution three-dimensional (3D) microscopy method that opens new possibilities for the microstructural investigation of fine-grained granular materials. Specifically, FIB-nt data volumes allow particle size distributions (PSD) to be determined, and the current paper discusses all the processing steps required to obtain the PSD from 3D data. This includes particle recognition and the subsequent PSD estimation. A refined watershed approach for 3D particle recognition that tolerates concavities on the particle surfaces is presented. Particles at the edge of the 3D data volume are invariably clipped, and because the data volume is of a very limited size, this effect of boundary truncation seriously affects the PSD and needs to be corrected. Therefore, two basic approaches for the stereological correction of the truncation effects are proposed and validated on artificially modeled particle data. Finally, the suggested techniques are applied to real 3D-particle data from ordinary portland cement and the resulting PSDs compared with data from laser granulometry. [ABSTRACT FROM AUTHOR]

Electrochemical performance of ceramic (Ni-free) SOFC anodes based on La 0.2 Sr 0.7 TiO 3-δ (LST) and Gd 0.1 Ce 0.9 O 1.95-δ (CGO) is thoroughly investigated. Microstructures and compositions are systematically varied around the percolation thresholds of both phases by modification of phase volume fractions, particle size distributions and firing temperature. Differential impedance spectroscopy was performed while varying gas composition, electrical potential and operating temperature, which allows determining four distinct electrode processes. Significant anode impedances are measured at low frequencies, which in contrast to the literature cannot be linked with gas concentration impedance. The dominant low frequency process (∼1 Hz) is attributed to the chemical capacitance. Combined EIS and microstructure investigations show that the chemical capacitance correlates inversely with the available surface area of CGO, indicating CGO surface reactions as the kinetic limitation for the dominant anode process and for the associated chemical capacitance. In anodes with a fine-grained microstructure this limitation is significantly smaller, which results in an impressive power output as high as 0.34 Wcm −2 . The anodes show high redox stability by not only withstanding 30 isothermal redox cycles, but even improving the performance. Hence, compared to conventional Ni-cermet anodes the new LST-CGO material represents an interesting alternative with much improved redox-stability. [ABSTRACT FROM AUTHOR]

The increase of ohmic losses caused by continuously growing Cr 2 O 3 scales on metallic interconnects (MICs) is a major contribution to the degradation of SOFC stacks. Comparison of measured ohmic resistances of chromium- (CFY) and ferritic-based alloy (Crofer) MICs at 850 °C in air with the growth of mean oxide scale thicknesses, obtained from SEM cross section images, reveals a non-trivial, non-linear relationship. To understand the correlation between scale evolution and resulting ohmic losses, 2D finite element (FE) simulations of electrical current distributions have been performed for a large number of real oxide scale morphologies. It turns out that typical morphologies favor nonhomogeneous electrical current distributions, where the main current flows over rather few “bridges”, i.e. local spots with relatively thin oxide scales. These current-“bridges” are the main reason for the non-linear dependence of ohmic losses on the corresponding oxide scale morphology. Combining electrical conductivity and SEM measurements with FE simulations revealed two further advantages: it permits a more reliable extrapolation of MIC-degradation data over the whole stack lifetime and it provides a method to assess the effective electrical conductivity of thermally grown Cr 2 O 3 scales under stack operation. [ABSTRACT FROM AUTHOR]

The ohmic resistance caused by Cr2O3 scale formation on metallic interconnects (MICs) can significantly contribute to the overall degradation of SOFC stacks. For this reason oxide scale growth on Cr5Fe1Y2O3 (CFY) and Fe22Cr0.5Mn (Crofer) was investigated by scanning electron microscopy (SEM) from post-test samples that were either exposed to air at 850 °C (furnace) or operated in Hexis planar SOFC-stacks under dual atmospheres (anode and cathode conditions) at temperatures around 900 °C. The study includes unique test results from a stack operated for 40,000 h. To analyze inhomogeneity in scale thicknesses a dedicated statistical image analysis method has been applied. SEM images were used to compare the structural phenomena related to MIC oxidation at different sample locations. The observed differences between different sample locations may relate to locally different conditions (temperature, pO2, H2O/O2-ratio). Cr2O3 scale growth on the anode side is found to be approximately twice as fast in comparison to the scale growth on cathode side. Finally, based on our time lapse analyses with extensive sampling it can be concluded that reliable predictions of scale growth requires statistical analyses over a period that covers at least a quarter (10,000 h) of the required SOFC stack lifetime (40,000 h). [ABSTRACT FROM AUTHOR]

Abstract: Chemical interactions between common electrolyte materials and various La doped strontium titanates (LST), which are redox-stable candidates for SOFCs anodes, were thoroughly investigated. The reactions of nanosized reagents were studied by SEM/EDX microscopy and XRD with subsequent Rietveld refinement. It was found that all A-site deficient LSTs promoted a reaction with Sc and Y stabilized zirconia, whilst stoichiometric LST was chemically stable. Detected structural and microstructural changes were solely assigned to high mobility of Ti. Diffusion of Ti into the zirconia structure promoted formation of tetragonal structures with p42/nmc-type space groups. The results indicate that the reduction of oxygen partial pressure during sintering and application of Sc-containing electrolyte material are successful strategies to hinder or even avoid reactivity. [Copyright &y& Elsevier]

Abstract: In this study A-site deficient lanthanum doped strontium titanate, which is considered as a promising, redox-stable candidate for full ceramic anodes in Solid Oxide Fuel Cells (SOFCs), was produced by nanoparticle-based spray pyrolysis. In this process cost-effective nitrate salts and titania nanoparticles are used as precursors. LST with a nominal composition of La0.2Sr0.7TiO3 showed limited stability at temperatures higher than 1290°C. It was observed that minor contents of secondary phases, which form at elevated temperatures, invoke a drastic loss of the electrical performance. Thermal stability is significantly increased by a slight enrichment of strontium. The phase pure A-site deficient LST shows remarkably higher electrical performance than similar stoichiometric counterparts. Reductive sintering results in a conductivity as high as 600Scm−1 at 600°C. Furthermore the A-site deficient LST shows a high redox-stability and fast redox-kinetics. With these properties LST is a suitable material for the fabrication of a new generation of Ni-free ceramic SOFC anodes. Secondary phases have a significant influence on the electrical conductivity and redox behaviour. [Copyright &y& Elsevier]

Reliable quantification and thorough interpretation of the degradation of solid oxide fuel cell (SOFC) stacks under real conditions is critical for the improvement of its long-term stability. The degradation behavior is often analyzed based on the evolution of current–voltage (V,I) curves. However, these overall resistances often contain unavoidable fluctuations in the fuel gas amount and composition and hence are difficult to interpret. Studying the evolution of internal repeat unit (RU) resistances is a more appropriate measure to assess stack degradation. RU-resistances follow from EIS-data through subtraction of the gas concentration impedance from the overall steady-state resistance. In this work a model-based approach where a local equilibrium model is used for spatial discretization of a SOFC stack RU running on hydrocarbon mixtures such as natural gas. Since under stack operation, fuel leakages, uneven fuel distribution and varying natural gas composition can influence the performance, they are taken into account by the model. The model extracts the time-dependent internal resistance from (V,I)-data and local species concentration without any fitting parameters. RU resistances can be compared with the sum of the resistances of different components that allows one to make links between laboratory degradation experiments and the behavior of SOFC stacks during operation. [ABSTRACT FROM AUTHOR]