Fundamentals of electro- and thermochemistry in the anode of solid-oxide fuel cells with hydrocarbon and syngas fuels

High fuel flexibility of solid-oxide fuel cells (SOFCs) affords the possibility to use relatively cheap, safe, and readily available hydrocarbon (e.g., CH4) or coal syngas (i.e., CO-H2 mixtures) fuels. Utilization of such fuels would greatly lower fuel cost and increase the feasibility of SOFC commercialization, especially for near-term adoption in anticipation of the long-awaited so-called “hydrogen economy”. Current SOFC technology has shown good performance with a wide range of hydrocarbon and syngas fuels, but there are still significant challenges for practical application. In this paper, the basic operating principles, state-of-the-art performance benchmarks, and SOFC-relevant materials are summarized. More in-depth reviews on those topics can be found in Kee and co-workers [Combust Sci and Tech 2008; 180:1207–44 and Proc Combust Inst 2005; 30:2379–404] and McIntosh and Gorte [Chem Rev 2004; 104:4845–65]. The focus of this review is on the fundamentals and development of detailed electro- and thermal (or simply, electrothermal) chemistry within the SOFC anode, including electrochemical oxidation mechanisms for H2, CO, CH4, and carbon, as well as the effects of carbon deposition and sulfur poisoning. The interdependence of heterogeneous chemistry, charge-transfer processes, and transport are discussed in the context of SOFC membrane-electrode assembly modeling.