TEM investigation on zirconate formation and chromium poisoning in LSM/YSZ cathode

Cell durability is a crucial technological issue for SOFC commercialization, and considerable progress has been made in recent years. A number of degradation pathways have been established, amongst which microstructural changes, poisoning effects and formation of less conductive phases. In this study, transmission electron microscopy was used to observe submicron-scale effects on selected cathode zones of an anode supported cell tested in SOFC stack repeat element configuration. The test has been performed with a dedicated segmented test bench, at 800°C for 1900h, which allowed to spatially resolve degradation processes, and therefore to improve their correlation with localized post-test analysis. Evidence is presented of reaction products (mainly SrZrO3) at the LSM/YSZ interfaces as well as of contaminants, in particular Cr, but also Si. A polarized cell segment is compared to an unpolarized one, to assess any influence of cathode polarizatio

Spotting Solid Oxide Fuel Cell Degradation Effects by Electron Microscopy

Extended abstract of a paper presented at Microscopy and Microanalysis 2012 in Phoenix, Arizona, USA, July 29 - August 2, 201

Electrochemical performance of Nd1.95NiO4+δ cathode supported microtubular solid oxide fuel cells

Nd1.95NiO4+δ (NNO) cathode supported microtubular cells were fabricated and characterized. This material presents superior oxygen transport properties in comparison with other commonly used cathode materials. The supporting tubes were fabricated by cold isostatic pressing (CIP) using NNO powders and corn starch as pore former. The electrolyte (GDC, gadolinia doped ceria based) was deposited by wet powder spraying (WPS) on top of pre-sintered tubes and then co-sintered. Finally, a NiO/GDC suspension was dip-coated and sintered as the anode. Optimization of the cell fabrication process is shown. Power densities at 750°C of ~40 mWcm-2 at 0.5V were achieved. These results are the first electrochemical measurements reported using NNO cathode-supported microtubular cells. Further developments of the fabrication process are needed for this type of cells in order to compete with the standard microtubular solid oxide fuel cells (SOFC).The authors thank grant MAT2009-14324-C02-01 and MAT2012-30763, financed by the Spanish Government (Ministerio de Ciencia e Innovación) and Feder program of the European Community, for funding the project.Peer Reviewe

Fabrication and performance of Nd1.95NiO4+δ (NNO) cathode supported microtubular solid oxide fuel cells

Trabajo presentado al 10th European Solid Oxide Fuell Cell Forum celebrado en Lucerna (Suiza) del 26 al 29 de Junio de 2012.Microtubular SOFC present significant advantages in comparison with the traditional planar SOFC configuration. In particular, the tubular design facilitates sealing and also reduces thermal gradients. As a consequence, rapid starts up times are possible. In addition, another advantage of the microtubular configuration is their higher power density per unit volume. Due to these properties, those devices are especially attractive for portable applications. There has been a great interest in microtubular SOFCs in the recent years, mainly using anode supported cells. Electrolyte supported cells have also been reported, but there are relatively few investigations using the cathode as the support. In the present paper, Nd1.95NiO4+δ (NNO) has been chosen as the cathode support, as it presents superior oxygen transport properties in comparison with other commonly used cathode materials, such as LSCF or LSM, and these material has been proven as an excellent cathode for SOFC and SOEC applications. Results on the fabrication and characterization of NNO cathode supported SOFC will be presented. The tubes were fabricated by cold isostatic pressing (CIP) using NNO powders and corn starch as the pore former. The electrolyte (GDC based) was deposited by wet powder spray (WPS) on top of the pre-sintered tubes and then co-sintered. Finally, a NiOGDC paste was dip-coated as the anode. Optimization of the fabrication process as well as the electrochemical performance of single cells will be further discussed.The authors thank grant MAT2009-14324-C02-01, financed by the Spanish Government (Ministerio de Ciencia e Innovación) and Feder program of the European Community, for funding the project. M.A.L.-B. thanks the JAE program (CSIC) for financial support.Peer Reviewe

Electrochemical Performance of Nd1.95NiO4+delta Cathode supported Microtubular Solid Oxide Fuel Cells

Nd1.95NiO4+delta (NNO) cathode supported microtubular cells were fabricated and characterized. This material presents superior oxygen transport properties in comparison with other commonly used cathode materials. The supporting tubes were fabricated by cold isostatic pressing (CIP) using NNO powders and corn starch as pore former. The electrolyte (GDC, gadolinia doped ceria based) was deposited by wet powder spraying (WPS) on top of pre-sintered tubes and then co-sintered. Finally, a NiO/GDC suspension was dip-coated and sintered as the anode. Optimization of the cell fabrication process is shown. Power densities at 750 degrees C of similar to 40 mWcm(-2) at 0.5V were achieved. These results are the first electrochemical measurements reported using NNO cathode-supported microtubular cells. Further developments of the fabrication process are needed for this type of cells in order to compete with the standard microtubular solid oxide fuel cells (SOFC)

Reduction of nickel oxide particles by hydrogen studied in an environmental TEM

In situ reduction of nickel oxide (NiO) particles is performed under 1.3mbar of hydrogen gas (H2) in an environmental transmission electron microscope (ETEM). Images, diffraction patterns and electron energy-loss spectra (EELS) are acquired to monitor the structural and chemical evolution of the system during reduction, whilst increasing the temperature. Ni nucleation on NiO is either observed to be epitaxial or to involve the formation of randomly oriented grains. The growth of Ni crystallites and the movement of interfaces result in the formation of pores within the NiO grains to accommodate the volume shrinkage associated with the reduction. Densification is then observed when the sample is nearly fully reduced. The reaction kinetics is obtained using EELS by monitoring changes in the shapes of the Ni L2,3 white lines. The activation energy for NiO reduction is calculated from the EELS data using both a physical model-fitting technique and a model-independent method. The results of the model-fitting procedure suggest that the reaction is described by Avrami models (whereby the growth and impingement of Ni domains control the reaction), in agreement with the ETEM observation

Quantitative study of anode microstructure related to SOFC stack degradation

As the performances of Solid Oxide Fuel Cells (SOFC) get attractive, long term degradation becomes the main issue for this technology. Therefore it is essential to localise the origin of degradation and to understand its processes in order to find solutions and improve SOFC durability. The electrode microstructure ageing, in particular nickel grain coarsening at the anode side, is known to be a major process to cause performance loss. The increase in nickel particle size will diminish the Triple Phase Boundary (TPB), where fuel oxidation takes place, and decrease the anode electronic conductivity. These two effects degrade the electrochemical performance of the fuel electrode. Degradation is defined as the decrease of potential at constant current density with time in %/1000h or mV/1000h. This study is based on HTceramix® anode supported cells tested in stack conditions from 100 to more than 1000 hours. The anode microstructure has been characterized by Scanning Electron Microscopy (SEM). As the back scattered electron yield coefficients of nickel and yttria stabilized zirconia (YSZ) are very close, the contrast of the different phases (Ni, YSZ and pores) is low. Various techniques are used to enhance the contrast. A new technique is presented here using impregnation and SEM observation based on secondary electron yield coefficients to separate the phases. Image treatment and analysis is done with an in-house Mathematica® code. Image treatment follows four steps: 1. inhomogeneous background correction, 2. double thresholding, 3. cleaning of the binary images and 4. reconstruction of a three-phase image. Image analysis gives information about phase proportion, particle size, particle size distribution, contiguity and finally a new procedure is developed to compute TPB density. A model to describe the coarsening of the nickel particles is also developed. The model assumes an exponential growth of the nickel particles. Using a particle population balance, it estimates the growth of the nickel particles and the concomitant drop in the TPB length. This model is in very good agreement with experimental data, especially for relatively low fuel cell operation times (up to 100-200 hours). This model can be used in the estimation of operational parameters of the anode electrode such as the degradation rate using fundamental parameters of the cermet anode like the anode overpotential and the work of adhesion of the nickel particles on the YSZ substrate. This model gives the portion of stack degradation that corresponds to anode performance decrease due to particle sintering. Finally this study gives the possibility to isolate the degradation coming from the anode sintering and compare to the full SOFC stack degradation

Nickel oxide reduction studied by environmental TEM and in situ XRD

Extended abstract of a paper presented at Microscopy and Microanalysis 2012 in Phoenix, Arizona, USA, July 29 - August 2, 201

Operando analysis of a solid oxide fuel cell by environmental transmission electron microscopy

Correlating the microstructure of an energy conversion device to its performance is often a complex exercise, notably in solid oxide fuel cell (SOFC) research. SOFCs combine multiple materials and interfaces that evolve in time due to high operating temperatures and reactive atmospheres. We demonstrate here that operando environmental transmission electron microscopy can simplify the identification of structure-property links in such systems. By contacting a cathode-electrolyte-anode cell to a heating and biasing microelectromechanical system in a single-chamber configuration, a direct correlation is found between the environmental conditions (O2 and H2 partial pressures, temperature), the cell voltage, and the microstructural evolution of the fuel cell, down to the atomic scale. The results shed new insights into the impact of the anode oxidation state and its morphology on the cell electrical properties.Comment: 18 pages, 5 figure