Publication date: 10th April 2024
Biogas is an important renewable energy resource that can be effectively converted into electrical energy using solid oxide fuel cells (SOFCs). Traditional Ni-YSZ cermet anodes are not suitable for operation with fuels such as natural gas or biogas due to fast degradation caused by coking and poisoning by ppm levels of H2S, a naturally occurring fuel impurity [1,2]. Perovskite-like oxides are considered a promising alternative to nickel with enhanced tolerance to carbon deposition and sulfur tolerance, although each candidate material has its advantages and drawbacks [1-3]. The aim of the present work is the evaluation of AVO3- and AMoO3-based oxides (A = Ca, Sr) as prospective anode components with an emphasis on the properties relevant for the anode applications.
Selected perovskite oxides including Sr(La)V(Nb)O3-δ, CaVO3-δ, PrVO3-δ and Sr(Mo,V,Ti)O3-δ were prepared under reducing conditions and assessed by a variety of techniques including measurements of electrical properties as a function of T-p(O2), determination of phase stability limits, electrical and dimensional changes on redox cycling, and behavior in presence of H2S and CH4. A(V,Mo)O3-δ-based components exhibit high electrical conductivity under fuel electrode operation conditions, up to 1000 S/cm. The phase stability domain of the perovskite phase is limited but can be extended by donor-type substitutions. While A(V,Mo)O3-δ have poor tolerance against H2S, substituted Sr(La)V(Nb)O3-δ and Sr(Mo,V,Ti)O3-δ perovskites as well as PrVO3-δ show a good stability in the presence of hydrogen sulfide. The introduction of a minor A-site deficiency has no positive effect on the phase stability limits or tolerance towards sulfur contamination. An example of composite electrode material prepared by in-situ reduction of oxidized precursors is demonstrated.
This work is supported by the grant 2020.04654.BD funded by the FCT and the project CICECO-Aveiro Institute of Materials (UIDB/50011/2020, UIDP/50011/2020 & LA/P/0006/2020) financed by national funds through the FCT/MCTES (PIDDAC).
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