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

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

A Review of RedOx Cycling of Solid Oxide Fuel Cells Anode

Abstract: Solid oxide fuel cells are able to convert fuels, including hydrocarbons, to electricity with an unbeatable efficiency even for small systems. One of the main limitations for long-term utilization is the reduction-oxidation cycling (RedOx cycles) of the nickel-based anodes. This paper will review the effects and parameters influencing RedOx cycles of the Ni-ceramic anode. Second, solutions for RedOx instability are reviewed in the patent and open scientific literature. The solutions are described from the point of view of the system, stack design, cell design, new materials and microstructure optimization. Finally, a brief synthesis on RedOx cycling of Ni-based anode supports for standard and optimized microstructures is depicted

Three-dimensional chemical analysis of laser-welded NiTi–stainless steel wires using a dual-beam FIB

The biomedical industry has an increasing demand for processes to join dissimilar metals, such as laser welding of NiTi and stainless steel wires. A region of the weld close to the NiTi interface, which previously was shown to be prone to cracking, was further analyzed by energy dispersive spectrometry (EDS) extended in the third dimension using a focused ion beam. As the spatial resolution of EDS analysis is not precise enough to resolve the finest parts of the microstructure, a new segmentation method that uses in addition secondary-electron images of higher spatial resolution was developed. Applying these tools, it is shown that this region of the weld close to the NiTi interface does not comprise a homogeneous intermetallic layer, but is rather constituted by a succession of different intermetallics, the composition of which can be directly correlated with the solidification path in the ternary Fe-Ni-Ti Gibbs simplex

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

Modification of textured silicon wafer surface morphology for fabrication of heterojunction solar cell with open circuit voltage over 700mV

Crystalline silicon wafer (c-Si) can be extremely well passivated by plasma enhanced chemical vapor deposited (PECVD) amorphous silicon (a-Si:H) films. As a result, on flat substrates, solar cells with very high open circuit voltage are readily obtained. On textured substrates however the passivation is more cumbersome, likely due to the presence of localized recombinative paths situated at the pyramid valleys. Here, we show that this issue may be resolved by selecting a silicon substrate morphology featuring large pyramids. Chemical post-texturization treatments can further reduce the surface recombination velocity. This sequence has allowed us to fabricate solar cells with open circuit voltage over 700 mV, demonstrating also on device level the effect of pyramid density and surface micro-roughness on the surface passivation quality

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