Minimizing Coke Formation at La0.3Ca0.7Fe0.7Cr0.3O3-δ Perovskite Anodes in a Syngas Fed-SOFC
Authors: Bass Adam Stuart , Singh Anand Chandra , Paulson Scott , Birss Viola Ingrid 
Published: February 2024

As the world moves to decarbonize the fossil fuel sector, transition technologies are needed that bridge the gap between natural gas power plants and more sustainable low-carbon energy sources. These newer technologies often still rely on fossil fuels but have improved energy conversion efficiencies and lower net carbon dioxide (CO2) outputs over conventional fossil fuel based electric power generation systems. In this work, we are exploring one such technology, namely the use of a syngas-fed solid oxide fuel cell (SOFC) to generate heat, electricity, steam, and captured CO2. Core to this technology is the mixed ion electron conductor deployed at the anode and cathode that catalyzes all of the relevant reactions, namely electrochemical oxidation of hydrogen (H2) and carbon monoxide (CO) at the anode, producing steam and CO2, and reduction of oxygen at the cathode.
Carbon formation (coking) is normally a significant problem affecting SOFCs operating on carbon-based fuels, as it leads to a rapid decline in electrochemical performance by blocking catalytically active sites and pores with various carbon species, e.g., amorphous, graphitic, or nanotubular carbon.1 The formation of carbon species from syngas is known to occur through various mechanisms, with the Boudouard reaction (∆H= -172 kJ/mol) and the reduction of CO (∆H= -131 kJ/mol) being the most prominent.2 As such, temperature is a key parameter to optimize as it determines the propensity for carbon formation at equilibrium. In addition, the kinetics of carbon formation can be significantly reduced by introducing oxygen to the fuel gas stream in the form of O2, CO2, or H2O.3

The catalyst materials investigated here are mixed conducting perovskite oxides (La0.3Ca0.7Fe0.7Cr0.3O3-
δ, LCFCr) that have been optimized and modified recently by our group, both in the as-prepared undoped form and after B-site doping with variable quantities of transition metals (M), e.g., Ni,4 forming nanoparticle (NP)-decorated ABO3-Mx surfaces. Our catalyst is highly active for H2 and CO oxidation, CO2 reduction, and O2 reduction, where it was demonstrated that the un-doped parent material can deliver a stable power density of 0.2 W/cm2 for several hundred hours with negligible performance degradation in 3% humidified H2.5 In more recent work, excellent resilience to carbon deposition for exsolved Fe-Ni@LCFCr up to 70:30 CO:CO2 was demonstrated.4 Herein, we show that minimal coke forms during exposure of these materials to dry syngas at 600oC, even under open circuit conditions.
The catalysts were prepared using combustion synthesis and were characterized by XRD, SEM EDX, and TPO-MS in order to confirm morphology, crystal structure, and composition as a function of temperature and gas environment.4 Symmetrical electrolyte-supported SOFCs were constructed using our catalyst as both the anode and cathode. Catalyst layers of 1 cm2 were screen printed to a thickness of 25 µm on both sides of commercially available 130 µm thick samaria-doped ceria (SDC)-buffered scandia-stabilized zirconia (ScSZ) electrolyte, followed by sintering at 1100°C for 2 h,4 with porous metal current collectors used. The cells were mounted and tested in a Fiaxel SOFC test station with gas flow controlled by mass flow controllers.
Preliminary electrochemistry experiments were conducted in 5:95 H2:N2, or 1:1 H2:CO (syngas) balanced by CO2 in a 1:2 ratio of fuel to oxidant into the anode chamber, and air into the cathode chamber at 600 oC, with performance evaluation carried out using CV, EIS and chronopotentiometry. The power density was found to be ca. 2x higher in dry H2 vs. in syngas, as expected, considering that H2 is a more active fuel vs. CO. Additionally, EIS exhibited ca. 2x higher resistance in the low frequency arc in syngas, which can be attributed to sluggish CO oxidation kinetics.4 Chronopotentiometry was performed for 20 h at 10 mA cm-2, showing a degradation rate of only 0.08 mV h-1, suspected to be primarily due to current collector delamination. Coking studies were also conducted on button cells at 600 oC in 1:1 H2:CO for 25 h at open circuit, comparing to a NiO standard that was painted on the electrolyte just next to the LCFCr-Ni working electrode. Imaging by SEM showed negligible carbon formation on the perovskite surface, supported by EDX analysis, compared to the extensive degree of coking observed at the standard. Further quantification was conducted by TPO-MS, also confirming minimal carbon formation.

References

Bengaard et al., Journal of Catalysis, 2002, 209, 365–384.

Farshchi Tabrizi et al., Energy Conversion and Management, 2015, 103, 1065–1077.

Sasaki et al., Journal of The Electrochemical Society, 2003, 150.

Ansari et al., Journal of Materials Chemistry A, 2022, 10, 2280–2294.

Addo et al., ECS Transactions, 2015, 66, 219–228.