Modelling-Assisted Investigation of Degradation Phenomena in LSM-based SOFC Composite Cathodes

This thesis focuses on the degradation pathways occurring in composite solid oxide fuel cell (SOFC) cathodes based on lanthanum-strontium manganite (LSM), combining modeling at the electrode level with experimental data. LSM composite electrodes are one of the most promising candidates for SOFCs cathodes, yet life-time is currently one of the limiting factors for the deployment of this technology. The combination of modelling tools and analysis of experimental data permitted to achieve a better comprehension of the mechanisms controlling the performance loss during operation and a quantification of the degradation. By acquisition and formalization of knowledge of degradation processes, this thesis offers new tools to predict the life-time of a cell, hypothesize technological solutions for limiting the performance losses, and evaluate the impact of such solutions. A new experimental strategy for SOFC button cell testing has been developed and validated during this work, namely the simultaneous operation of several cathode segments on the same cell support. This allowed, on the one hand, the production of reproducible and reliable data for the evaluation and investigation of degradation processes and, on the other hand, the possibility of rapid identification of experimental problems affecting one segment. The approach has been validated both experimentally and theoretically – through finite element calculations. The vast majority of the experimental results contained in this work has been obtained using this testing configuration. Furthermore, investigation techniques with unprecedented resolution in the SOFC research field have been developed in collaboration between EPFL and external partners, namely a fast Cr quantification in operated cells, and 3D non-destructive reconstruction of cathode microstructures by X-ray computed tomography, giving new instruments for the study of SOFC performance and degradation. Finally, a set of data has been gathered concerning the reactivity of LSM-based systems, aging composite pellets for different times and temperatures and analyzing them with Rietveld-XRD, in order to map and assess the loss of performance caused by the formation of insulating phases in the electrode. A steady-state electrode model present in literature has been selected and improved for simulating the performance of composite cathodes in presence of degradation phenomena, converting it into a time-dependent model. The first phenomenon that has been integrated is the variation of the microstructure of the composite electrode, allowing the prediction of variation in performance for a number of case studies: coarsening of only one phase, coarsening of both phases, coarsening of both phases with variation of porosity. Experimental results obtained by microstructural analysis and electrochemical characterization of cells aged for different times were compared to the simulations of the correspondent case study, showing that the morphological variation of the anode electrode in the early cell operation (first few hundreds hours) is well predicted by the time-dependent model. No cathode morphological variation on this time scale could be detected. Another degradation pathway analyzed was poisoning by Cr species. The phenomenon has been modelled assuming an overpotential-driven deposition of Cr blocking species on the electrode active sites. Validation has been performed comparing the simulations to Cr pro les obtained experimentally from cell tested for relatively short time (1000 h); one conclusion reached was that increased electrode thickness has a beneficial effect in limiting Cr poisoning. The simulation was extended to operation times on the order of several 10 kh, difficult to achieve experimentally, describing the progressive deactivation of the electrode material. The model provides an estimation of the expected life-time of an electrode and predicts quantitatively the performance loss during time; this allows individuating technological solutions to hinder Cr poisoning, and the evaluation of the impact of such solutions. In particular, it has been found that the conductivity and amount of the electrolyte phase are critical, and that a three-fold decrease of the degradation related to Cr poisoning is expected while passing from 50%LSM/50%YSZ (standard composition for most LSM based cathodes) to 42%LSM/58%ScSZ electrodes (new composition). Finally, it has been found that cathode composition may have an indirect effect on the amount of deposited Cr: experimental evidences supporting a Mn-catalyzed deposition of Cr species have been found, suggesting that the presence of excess Mn in the cathode system can be detrimental.

Self and induced stabilized nanoparticles for electrocatalysis

Mériadec Limat

Since few decades the search of new catalysts formulations for fuel cell applications has motivated numerous projects especially due to the future lack of fossil fuel, environmental and economical reasons. Consequently, Direct Alcohol Fuel Cell (DAFC) or Direct Formic Acid Fuel Cell domains have received great attention. In spite of the promising results reported recently, these types of fuel cell still exhibit some problems. In fact, platinum, bulk or nanoparticles, undergoes surface poisoning involved by intermediates (as acetaldehyde, acetic acid, carbon monoxide) which are strongly bonded to the surface. These poisoning species block the active sites at the surface electrode and drastically decrease the catalytic activity and also the life-time of the cell. Probable solutions are suggested essentially in Pt-based alloys catalysts or nanocatalysts in order to avoid this phenomenon. Therefore, multicomponent catalysts deposited at carbon electrodes (Boron-Doped Diamond and Highly Oriented Pyrolytic Graphite) has been investigated during this thesis. These two substrates have been chosen due to their outstanding properties. In the first part of this study, self stabilized nanoparticles at BDD substrate have been studied. Ex-situ ternary Pt-Ru-Sn microemulsion-synthesized nanoparticles deposited at BDD substrate were investigated towards both methanol and ethanol electrooxidation. Such type of composite electrode seemed to possess a greater efficiency towards methanol oxidation than observed for ethanol, leading essentially for the latter to C2 oxidation products. The inability of this catalyst to activate the C-C bond scission can explain this observation. However, the major enhancement was observed for the methanol electrooxidation. Recent studies have shown that gold nanoparticles exhibited surprising catalytic activity, very different from the bulk, making them a privileged candidate to replace or be added to platinum. Gold nanoparticles prepared with a twofold technique (sputtering followed by a heat treatment in air) have been characterized with both outer and inner-sphere redox reactions. It has been observed that the resulting electrochemical behavior of such type of composite electrode was similar to a gold microelectrodes array, due to the high difference between the two material electrochemical rate constants. In a morphological point of view, the processes of nucleation and growth engaged in the stabilized and well-dispersed gold nanoparticles formation have especially attracted a great attention. At BDD surface, the gold nanoparticles were located at specific sites (grain boundaries, defects, impurities,…). This phenomenon has motivated further investigations at HOPG substrate, known to possess a quite smooth and perfect surface. In the second part of this thesis, induced stabilized nanoparticles at HOPG surface were studied. In a first time, HOPG was morphologically and electrochemically characterized. The surface state has appeared to be a key parameter, essentially with the presence of the two surface species, the edge plane and the basal plane. High modifications in the electrochemical behavior of HOPG electrode were observed after an anodic pretreatment in acidic media, due to surface concentration increase of the edge plane species, which are highly reactive. Based on these results a tailoring of the HOPG has been performed in order to create nanocontainers for a further gold deposition. HOPG surface has been bombarded by gold clusters and then oxidized (etching step) under well-defined experimental conditions, leading in a tailored pattern of nanopits with high reliability and reproducibility. Gold deposition was performed by evaporation. The gold nanoparticles were located in the created nanocontainers and were found to be stable under cyclic voltammetric measurements in acidic media. A new synthesis method for a bimetallic or alloy system formed by Au and Pt nanoparticles stabilized at tailored HOPG surface was developed. Pt electrodeposited at Au/HOPG electrode surface have been observed to preferentially deposit on Au. In fact, gold nanoparticles were used as nucleation sites for the platinum particles. The resulting Pt-Au/HOPG electrodes were then heated at 400 °C in vacuum conditions to improve interactions between both metals. The appearance of an alloy was observed and characterized by a negative shift in the peak potential of Pt oxides reduction. Thanks to these results, Pt-Au/HOPG composite electrodes were applied for electrocatalytic oxidation. At a surface composition of P55-Au45 alloy, Pt-Au/HOPG after the heat treatment has demonstrated a higher electrocatalytic activity than before the heat treatment towards formic acid electrooxidation. It seemed that electronic and geometrical effect was responsible of such enhancement. Finally, bismuth adsorption at both P55-Au45/HOPG and polycrystalline platinum was investigated towards formic acid electrooxidation. The effect of Bi adatoms has been essentially ascribed to geometrical restrictions for CO to adsorb at platinum active sites. Drastic enhancement in current density at a fixed potential and dramatic decrease of the onset potential of formic acid oxidation were observed. Thus, it seemed that avoiding the CO poisoning can be the most judicious development for new electrocatalysts in fuel cell applications.

EPFL2009

Préparation et caractérisation de nanoparticules bimétalliques (Pt-Au) sur un substrat en diamant dopé au bore

Bahaa El Roustom

Using petrol as a main source of energy, during the 20th century, has caused considerable amounts of damage among which are atmospheric pollution and global warming. At the same time, many geologists and economists expect that the discovery rate of new petrol sources will not follow the market's demand causing a serious shortage of petrol in the near future. These alarming perspectives have motivated scientists around the world to develop new clean and renewable energy sources. It is in that objective that electrochemists intensified their research in order to develop the fuel cell technology. This latter consists in directly converting chemical energy into electricity. The main advantage of this technology over traditional energy production is that the fuel cell energy efficiency is Carnot cycle independent. The theoretical efficiency of such an energy source is nearly 90%. Direct Alcohol Fuel Cell (DAFC), fed by ethanol on one hand and by air (oxygen) in the other hand, is a very interesting option for such kind of energy production. Ethanol is a renewable energy source of vegetal origin whose CO2 production is consumed by plants during the cycle. Even though Pt has long been known to be a perfect catalyst for DAFC, it has some principal limitations, the most important ones being poisoning by intermediate products (OH on the cathodic side and CO on the anodic side) and a relatively high cost compared to other materials. These problems have pushed the experts in the field to focalize their research on the development of more suitable and better performing materials. Gold nanoparticles have shown a surprising catalytic activity, very different from the bulk, making them a preferential candidate to replace Pt. A system based on using two or more metals as catalysts (example Au-Pt) dispersed on an appropriate substrate seems to be also an interesting candidate to enhance the cell's efficiency. The substrate should be chemically inert, non-oxydable and should not present any interference with the electrochemical and electrocatalytic behaviour of the nanoparticles. In the first part, the employed substrate, which is boron doped diamond (BDD) is characterized. The substrate's main characteristics are its chemical inertness, its weak residual current and its resistance to corrosion. These characteristics contribute to making the substrate an ideal support for nanoparticles. In this work, the substrate is a diamond film, but for fuel cell applications diamond should be used as powder or dispersed particles. In chapters III and IV, we studied the effect of boron incorporation on the morphology and the behaviour of the diamond film. For this purpose, samples with different ratios of boron/carbon (B/C) in the vapour phase during preparation were characterized (B/C = 300, 1000, 2500 and 6000 ppm). Results showed that the grain size decreases with increasing boron content in the film. This is accompanied by a transition towards a quasi-metallic character. It was also found that graphitic impurities in the diamond film increase when the B/C ratio increases. We also established some graphitic impurities increase in the diamond film when the ratio of B/C increases. The identity of these impurities was established in chapter III as being surface redox couples (semi-quinone/semi-hydroquinone). Using cyclic voltametry we were able to observe a total elimination (B/C=300 ppm) or partial elimination (B/C=6000 ppm) of these surface redox couples. We also found in chapter IV that these surface redox couples are responsible of the electrochemical activity of the BDD electrode. BDD electrodes with different doping level B/C=300, 1000 and 6000 ppm) in the vapour phase are modified with IrO2 nanoparticles using the method of thermal decomposition. Our results showed that, at low potentials, the behaviour of the composite electrode IrO2/BDD with respect to the reaction of oxygen evolution is independent of the doping level. On the other hand, at high potentials, the weakly doped electrode (B/C=300 ppm) presents a supplementary overpotential due to the interface BDD-IrO2. An approach based on the double junction is developed in this work describing two distinct behaviours depending on the boron concentration in the diamond film. A new method for Au nanoparticles deposition on highly doped BDD electrodes (B/C= 2500 ppm) is presented in chapter VI. This method involves two steps: the first step consists on sputtering the equivalent of few nanolayers of Au on the diamond surface; the second step is a heat treatment in air at high temperatures. Several parameters that could influence the dispersion, the stability as well as the diameter of the Au nanoparticles are studied. In chapter VII, the behaviour of the composite electrode Au/BDD is studied in a solution containing redox couples in acid media. This electrode was simulated as an arrangement of active Au microelectrodes dispersed on a less active BDD substrate. The overall behaviour of the composite electrode (Au/BDD) has been related to the electrochemical rate constants on each material. In chapter VIII, another new synthesis method for a bimetallic system formed by Au and Pt nanoparticles dispersed on a BDD substrate is developed. This method consists in electrodepositing a small amount of Pt on a composite electrode Au/BDD. Our results showed that Pt was preferentially deposited on Au covering its whole surface. In fact, Au nanoparticles serve as germ of nucleation for Pt. In the following step, the bimetallic PtbAu/BDD is heated to 400°C in air to enhance the interaction between Au and Pt. The experiments showed that Au reappeared on the surface. The electrochemical behaviour of the bi-metallic electrode is characterized by a negative shift in the peak potential of reduction of Pt oxides. This is not the case of heterogeneous alloys obtained by the fusion of two metals at high temperatures. The composite electrode Au/BDD as well as the bi-metallic electrode Pt-Au/BDD are used for electrocatalytic applications. The studied reaction in chapter IX is the oxygen reduction reaction (ORR) in an acid medium. We found that the number of exchanged electrons increases with increasing the amount of Pt at the surface. Oxygen is reduced into H2O2 on the Au/BDD electrode and into H2O on the Pt-Au/BDD electrode. In chapter X we studied the reaction of oxidation of oxalic acid. The behaviour of both Au and Pt electrodes seemed very similar for this reaction. The bi-metallic electrode containing both Pt and Au on its surface has shown an intermediate behaviour between the behaviour of the two metals.

EPFL2006

Segmented cell testing for cathode parameter investigation

Christos Comninellis, Josef Andreas Schuler, Pietro Tanasini, Jan Van Herle, Zacharie Wuillemin

The increasing quality and durability of Solid Oxide Fuel Cells (SOFC) state-of-the-art materials renders the long-term testing of fuel cells difficult since considerably long equipment times are needed to obtain valuable results. Moreover, reproducibility issues are common due to the high sensitivity of the performance and degradation on the testing conditions. An original segmented cell configuration has been adopted in order to carry out four tests in parallel, thus decreasing the total experimental time and ensuring the same operating conditions for the four segments. The investigation has been performed on both anode-supported cells and symmetrical Lanthanum-Strontium Manganite – Yttria-Stabilized Zirconia (LSM-YSZ) electrolyte-supported cells. In separate tests, the influence of variables like cathode thickness, current density and cathode composition on performance and degradation have been explored on anode supported cells. Furthermore, the effect of chromium poisoning has been studied on electrolyte-supported symmetric cells by contacting one segment with a chromium-iron interconnect material. Long-term polarization of the segments is controlled with a multi-channel galvanostatic device designed in-house. Electrochemical characterization has been performed through Electrochemical Impedance Spectroscopy (EIS) at different H2 partial pressures, temperatures and bias current, effectively demonstrating the direct impact of each studied variable on the cell performance and degradation behaviour. Segmented cell testing has been proven to be an effective strategy to achieve high reproducibility for SOFC measurements since it avoids the inevitable fluctuations found in a series of successively run tests. Moreover, simultaneous testing increased n-fold the data output per experiment, implying a considerable economy of time.

European Fuel Cell Forum 20102010