The development of alternative cathodes for high temperature solid oxide electrolysis cells
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This study mainly explores the development of alternative cathode materials for the electrochemical reduction of CO₂ by high temperature solid oxide electrolysis cells (HTSOECs), which operate in the reverse manner of solid oxide fuel cells (SOFCs). The conventional Ni-yttria stabilized zirconia (YSZ) cermets cathode suffered from coke formation, whereas the perovskite-type (La, Sr)(Cr, Mn)O₃ (LSCM) oxide material displayed excellent carbon resistance. Initial CO₂ electrolysis performance tests from different cathode materials prepared by screen-printing showed that LSCM based cathode performed poorer than Ni-YSZ cermets, due to non-optimized microstructure. Efforts were made on microstructure modification of LSCM based cathodes by means of various fabrication methods. Among the LSCM/YSZ graded cathode, extra catalyst (including Pd, Ni, CeO₂, and Pt) aided LSCM/GDC (Gd₀.₁Ce₀.₉O₁.₉₅) cathode, LSCM impregnated YSZ cathode, and GDC impregnated LSCM cathode, the GDC impregnated LSCM cathode, with porous LSCM as backbone for finely dispersed GDC nanoparticles, was found to possess the desired microstructure for CO₂ splitting reaction via SOEC. Incorporating of 0.5wt% Pd into GDC impregnated LSCM cathode gave rise to an Rp of 0.24 Ω cm² at open circuit voltage (OCV) at 900°C in CO₂-CO 70-30 mixture, comparable with the Ni/YSZ cermet cathode operated in the identical conditions. Meanwhile, the cathode kinetics and possible mechanisms of the electrochemical reduction of CO₂ were studied, and factors including CO₂/CO composition, operation temperature and potential were taken into account. The current-to-chemical efficiency of CO₂ electrolysis was evaluated with gas chromatography (GC). The high performance Pd and GDC co-impregnated LSCM cathode was also applied for CO₂ electrolysis without protective CO gas in feed. This cathode also displayed superb performance towards CO₂ electrochemical reduction under SOEC operation condition in CO₂/N₂ mixtures, though it had OCV as low as 0.12V at 900°C. The LSCM/GDC set of SOEC cathode materials were investigated in the application of steam electrolysis and H₂O-CO₂ co-electrolysis as well. For the former, adequate supply of steam was essential to avoid the appearance of S-shaped I-V curves and limited steam transport. The 0.5wt% Pd and GDC co-infiltrated LSCM material has been found to be a versatile cathode with high performance and good durability in SOEC operations.
Thesis, PhD Doctor of Philosophy
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