Comparison of Operating Atmosphere Impact on La0.7Sr0.3V3.86-⸹ (LSV) Intermediate-Temperature Solid Oxide Fuel Cell Sulfur Tolerance Explored Through Experimental and Modeling Characterization Over Time
Authors: Burye Theodore , Sebastian Talia 
Published: November 2022

Experts have long projected that in the future solid oxide fuel cells (SOFCs) could provide a viable path for the replacement of existing power sources and the production of clean, secure, and sustainable energy. Today, not only have SOFCs matured as a technology with a proven ability to provide high density, high efficiency power with long term stability at low cost and environmental impact, but with the theoretical capacity to utilize a variety of naturally sourced fuels. This theoretical capacity makes their potential use attractive in many additional applications and positions SOFCs to be the technology which can bridge the gap between current hydrocarbon fueled technologies and future hydrocarbon fueled electric technologies. That said, there remains many technical hurdles associated with the incorporation of naturally sourced fuels, to include thermal stress cracking and catalyst coarsening, delamination, and poisoning. Catalyst poisoning, specifically arising from sulfur impurities in naturally sourced fuels, remains one of the largest SOFC technical challenges, since their presence, even at low concentrations, have now shown permanent performance degradation. As the U.S. Army begins to investigate SOFCs to enable additional capabilities like silent watch, advanced radios, and exportable power in their fleet, catalyst poisoning from sulfur impurities presents a concerning technology gap which must be addressed, as the entire fleet operates on JP-8 kerosene-based fuel, which by specification can contain up to 3000 ppm of sulfur, via AR-70 single fuel policy.

As SOFC technologies migrate to lower temperature operation to resolve physical degradation issues, the development catalysts materials with greater sulfur tolerance are being explored to resolve issues of chemical degradation related to sulfur poisoning. In this study, a previously reported, high temperature, sulfur tolerant SOFC catalyst, La0.7Sr0.3VO3.86-⸹ (LSV), was further experimentally investigated via Optical Microscopy, X-ray Diffraction, Scanning Electron Microscopy and Energy Dispersive Spectroscopy for its sulfur tolerance at currently targeted SOFC intermediate operating temperatures (400-600°C) in wide range of hydrogen sulfide (30ppm, 300ppm and 10vol%) balance hydrogen gas environments for up to 100 hours. When compared against the industry standard Ni-YSZ anode, LSV was observed to have significantly lower (287x) sulfur adsorption rates, with the lowest rates observed between 600-700°C. This behavior is attributed the cubic structure the material presents in this temperature range. Higher adsorption rates were observed in the monoclinic/tetragonal structure the material presents at temperatures between 400-500°C. This study was further supplemented by a theoretical investigation of hydrogen sulfide adsorption on low index LSV surfaces via periodic Density Functional Theory. When compared against Ni-YSZ, which is known to accumulate sulfur from hydrogen sulfide via two-step dissociative adsorption, LSV was observed to accumulate sulfur through weak chemisorption (0.43 eV max) of undissociated molecular hydrogen sulfide only. The weak chemisorption behavior is attributed to structural surface changes due to oxygen vacancies near strontium defects, wherein the strongest adsorption energies were observed, and in direct contrast to similar calculations of hydrogen sulfide adsorption with low index surfaces of LVO3, wherein no adsorption was observed.

Since it is likely SOFCs will operate on hydrocarbon fuels, as well as compressed hydrogen gas in the future, this study is also currently experimentally investigating sulfur accumulation under the same operating conditions above with hydrogen sulfide mixtures in methane gas. Methane is a small hydrocarbon chain, which will help minimize the accumulation of carbon deposition. Initial comparisons of sulfur adsorption between hydrogen and methane gas mixtures, using low hydrogen sulfide concentrations, show they are statistically similar, although methane gas exposure was observed to result in the formation of two activation energies, which was not observed with hydrogen mixture previously. The methane gas was also observed to promote LSV to take the monoclinic/tetragonal structure at lower operating temperatures than hydrogen mixtures. This observation may lead to elevated sulfur adsorption rates at higher hydrogen sulfide concentrations. Finally, it was originally observed during experimental exposure experiments with hydrogen sulfide/hydrogen gas balance mixtures that higher concentrations of lattice oxygen, present at lower temperatures, had a positive correlation with sulfur accumulation in the LSV material. This study is therefore currently theoretically investigating the effect of lattice oxygen content on the LSVs structure via Density Functional Theory, which could lead to further derivation from optimal cubic configuration, which may lead to configurations which increase sulfur adsorption.

Figure 1