Activation of H(2) oxidation at sulphur-exposed Ni surfaces under low temperature SOFC conditions.

Abstract

Ni-YSZ (yttria-stabilized zirconia) cermets are known to be very good anodes in solid oxide fuel cells (SOFCs), which are typically operated at 700-1000 °C. However, they are expected to be increasingly degraded as the operating temperature is lowered in the presence of H2S (5-10 ppm) in the H2 fuel stream. However, at 500 to 600 °C, a temperature range rarely examined for sulphur poisoning, but of great interest for next generation SOFCs, we report that H2S-exposed Ni-YSZ anodes are catalytic towards the H2 oxidation reaction, rather than poisoned. By analogy with bulk Ni3S2/YSZ anodes, shown previously to enhance H2 oxidation kinetics, it is proposed that a thin layer of Ni sulphide, akin to Ni3S2, is forming, at least at the triple point boundary (TPB) region under our conditions. To explain why Ni3S2/YSZ is so active, it is shown from density functional theory (DFT) calculations that the O(2-) anions at the Ni3S2/YSZ TPB are more reactive towards hydrogen oxidation than is O(2-) at the Ni/YSZ TPB. This is accounted for primarily by structural transformations of Ni3S2 during H2 oxidation, rather than by the electronic properties of this interface. To understand why a thin layer of Ni3S2 could form when a single monolayer of sulphur on the Ni surface is the predicted surface phase under our conditions, it is possible that the reaction of H2 with O(2-), forming water, prevents sulphur from re-equilibrating to H2S. This may then promote Ni sulphide formation, at least in the TPB region.

• Authors: Lisa Deleebeeck, Maxim Shishkin, Paul Addo, Scott Paulson, Hebert Molero, Tom Ziegler, Viola Birss
• Journal: Physical chemistry chemical physics : PCCP (Phys Chem Chem Phys) Vol. 16 Issue 20 Pg. 9383-93 (May 28 2014) ISSN: 1463-9084 [Electronic] England
• PMID: 24718381 (Publication Type: Journal Article)