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The combination of fossil-derived fuels with ethanol and methanol has acquired relevance and attention in several countries in recent years. This trend is strongly affected by market prices, constant geopolitical events, new sustainability policies, new laws and regulations, etc. Besides bio-fuels these materials also include different additives as anti-shock agents and as octane enhancer. Some of the chemical compounds in these additives may have harmful properties for both environment and public health (besides the inherent properties, like volatility). We present detailed Raman spectral information from toluene (C7H8) and ethanol (C2H6O) contained in samples of ElO gasoline-ethanol blends. The spectral information has been extracted by using a robust, high resolution Fourier-Transform Raman spectrometer (FT-Raman) prototype. This spectral information has been also compared with Raman spectra from pure additives and with standard Raman lines in order to validate its accuracy in frequency. The spectral information is presented in the range of 0 cm-1 to 3500 cm-1 with a resolution of 1.66cm-1. This allows resolving tight adjacent Raman lines like the ones observed around 1003cm-1 and 1030cm-1 (characteristic lines of toluene). The Raman spectra obtained show a reduced frequency deviation when compared to standard Raman spectra from different calibration materials. The FT-Raman spectrometer prototype used for the analysis consist basically of a Michelson interferometer and a self-designed photon counter cooled down on a Peltier element arrangement. The light coupling is achieved with conventional62.5/125μm multi-mode fibers. This FT-Raman setup is able to extract high resolution and frequency precise Raman spectra from the additives in the fuels analyzed. The proposed prototype has no additional complex hardware components or costly software modules. The mechanical and thermal disturbances affecting the FT-Raman system are mathematically compensated by accurately extracting the optical path information of the Michelson interferometer. This is accomplished by generating an additional interference pattern with a λ = 632.8 nm Helium-Neon laser (HeNe laser). It enables the FT-Raman system to perform reliable and clean spectral measurements from the materials under observation.
The formation of secondary phases in the porous electrodes is a severe mechanism affecting the lifetime of solid oxide fuel cells (SOFC). It can occur via various chemical mechanisms and it has a significant influence on cell performance due to pore clogging and deactivation of active surfaces and triple-phase boundary (TPB). We present a modeling and simulation study of nickel oxide formation (reoxidation) and carbon formation (coking) within the SOFC anode. We use a 2D continuum model based on a multi-phase framework [Neidhardt et al., J. Electrochem. Soc., 159, 9 (2012)] that allows the introduction of arbitrary solid phases (here: Ni, YSZ, NiO, Carbon) plus gas phase. Reactions between the bulk phases are modeled via interface-adsorbed species and are described by an elementary kinetic approach. Published experimental data are used for parameterization and validation. Simulations allow the prediction of cell performance under critical operation conditions, like (i) a non-fuel operation test, where NiO formation is taking place (Figure 1a), or (ii) an open circuit voltage (OCV) stability test under hydrocarbon atmosphere, where solid carbon is formed (Figure 1b). Results are applied for enhanced interpretation of experimental data and for prediction of safe operation conditions.
In the dual membrane fuel cell (DM-Cell), protons formed at the anode and oxygen ions formed at the cathode migrate through their respective dense electrolytes to react and form water in a porous composite layer called dual membrane (DM). The DM-Cell concept was experimentally proven (as detailed in Part I of this paper). To describe the electrochemical processes occurring in this novel fuel cell, a mathematical model has been developed which focuses on the DM as the characteristic feature of the DM-Cell. In the model, the porous composite DM is treated as a continuum medium characterized by effective macro-homogeneous properties. To simulate the polarization behavior of the DM-Cell, the potential distribution in the DM is related to the flux of protons and oxygen ions in the conducting phases by introducing kinetic and transport equations into charge balances. Since water pressure may affect the overall formation rate, water mass balances across the DM and transport equations are also considered. The satisfactory comparison with available experimental results suggests that the model provides sound indications on the effects of key design parameters and operating conditions on cell behavior and performance.