Electrochemical behavior of thin-film Sm-doped ceria: insights from the point-contact configuration
The electrochemical behavior of chemical vapor deposition (CVD) grown porous films of Sm-doped ceria (SDC) for hydrogen oxidation has been evaluated by impedance spectroscopy using a point contact geometry at a temperature of 650 °C. Porous SDC films, 950 nm in thickness, were deposited on both sides of single-crystal YSZ(100). Pt paste was applied over the surface of one SDC layer to create a high-activity counter electrode. Ni wire was contacted to the surface of the other SDC layer to create a limited contact-area working electrode. The active area of contact at the working electrode was determined using the Newman equation and the electrolyte constriction impedance. The radius of this area varied from 5 to 18 μm, depending on gas composition and bias. The area-normalized electrode impedance (where the area was that determined as described above) varied from 0.03 to 0.17 Ω cm^2 and generally decreased with cathodic bias and decreasing oxygen partial pressure. From an analysis of the dimensions of the active area with bias, it was found that the majority of the overpotential occurred at the SDC|gas interface rather than the SDC|YSZ interface. Overall, the anode overpotential is found to be extremely small, competitive with the best oxide anodes reported in the literature. Nevertheless, the impedance falls in line with expected values based on extrapolations of the properties of dense, flat SDC model electrodes grown by pulsed laser deposition (Chueh et al., Nat. Mater., 2012). The results demonstrate that, with suitable fabrication approaches, exceptional activity can be achieved with SDC for hydrogen electrooxidation even in the absence of metal–oxide–gas triple phase boundaries.
© 2015 the Owner Societies. Received 20 Dec 2014, Accepted 20 Apr 2015. First published online 21 Apr 2015. Financial support for this work was provided by the Stanford Global Climate and Energy Project (GCEP), for which we express our gratitude. We thank Prof. William Chueh (Stanford University) and Yong Hao (Institute of Engineering Thermophysics, CAS) for valuable discussions. Prof. Raymond Gorte (Univ. of Penn.) generously provided access to materials characterization facilities at Univ. of Penn. This work builds on the insights and timeless optimism of the late David G. Goodwin.
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