Annabelle Brisse

Syngas production via high-temperature steam/CO2 co-electrolysis: an economic assessment

Although it is not yet technologically mature, the high-temperature steam/CO2 co-electrolysis process offers potentially a feasible and environmentally benign way to convert carbon-free or low-carbon electrical energy into chemical energy stored in syngas with a desired H2 to CO ratio for further processing. An attractive application is to convert the as-produced syngas further into synthetic liquid fuels through the Fischer–Tropsch (F-T) process. The synfuel can be used as alternative fuels in the transportation sector while keeping the existing infrastructure and motor engine technology unchanged. The combination of the high-temperature steam/CO2 co-electrolysis process and the F-T process thus offers an efficient way to store electricity in transportation fuels. The implementation of such a quasi carbon-neutral process depends on its economic competitiveness. In the present paper, an economic assessment of this process is performed through process modelling and sensitivity analysis. As an energy-intensive process, the availability of cost-effective electricity is crucial for its economic competitiveness. Preferred electricity sources are probably nuclear power and surplus wind power, with which synthetic fuels could be produced at a cost comparable to BTL (Biomass to Liquid) process. The present process is biomass-independent, and can also be located in regions where solar energy is abundant.

Electronic Conduction of Yttria-Stabilized Zirconia Electrolyte in Solid Oxide Cells Operated in High Temperature Water Electrolysis

Anode-supported solid oxide fuel cells with yttria-stabilized zirconia (YSZ) electrolytes, both commercial and research, are used at 800-900°C as solid oxide H 2 O electrolyzer cells (SOECs). When the operation is extended to current densities j corresponding to a steam-conversion rate above 100%, or when the steam supply is interrupted under constant current conditions, cell voltages saturate at ~ 1.9 V at 810°C. A cell survives 64 h polarization at j = -0.34 A cm -2 without any steam supply. The mechanism limiting the cell voltage is attributed to electronic conduction in the YSZ electrolyte. No indications are found for electrolyte decomposition. Because the saturation voltage exceeds typical operation voltages by several hundred millivolts, electrolyte conduction in the normal SOEC mode remains predominantly ionic. The rise in the cell voltage to the value determined by electronic conduction occurs when steam transport in the hydrogen/steam electrode becomes limiting. As a consequence of H 2 O back-diffusion from the cell exhaust in the used unsealed test configuration, the rise occurs at nonzero current density under zero steam supply. Impedance spectroscopic data are compared with and without steam supply and are qualitatively interpreted with an equivalent circuit model.

In situ Reduction and Oxidation of Nickel from Solid Oxide Fuel Cells in a Transmission Electron Microscope

Environmental transmission electron microscopy was used to characterize in situ the reduction and oxidation of nickel from a Ni/YSZ solid oxide fuel cell anode support between 300-500°C. The reduction is done under low hydrogen pressure. The reduction initiates at the NiO/YSZ interface, then moves to the center of the NiO grain. At higher temperature the reduction occurs also at the free NiO surface and the NiO/NiO grain boundaries. The growth of Ni is epitaxial on its oxide. Due to high volume decrease, nanopores are formed during reduction. During oxidation, oxide nanocrystallites are formed on the nickel surface. The crystallites fill up the nickel porosity and create an inhomogeneous structure with remaining voids. This change in structure causes the nickel oxide to expand during a RedOx cycle.

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 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.