(Invited) Proton Surface Exchange Kinetics and Stability of Thin-Film Triple Conducting Oxides for Protonic Ceramic Electrolysis Cells

Abstract

Protonic ceramic electrolysis cells (PCECs) have been attracting attention due to their ability to operate in the intermediate temperature (300 - 500 ˚C) sweet-spot. These temperatures enable fast kinetics, inexpensive materials (no precious metals; stainless interconnects), and lower operating voltage for producing green hydrogen, without the accelerated degradation that may be observed at higher temperatures. The steam electrodes often support triple conduction and thereby host the proton exchange / oxygen evolution process at the surface, where steam is split. Steam electrode materials development is at a relatively early stage, with open questions around the relationships among bulk composition, evolving surface chemistry, kinetic quantities, and degradation mechanisms. We are investigating the proton exchange surface coefficient (k) and its evolution over time on model thin film electrodes in order to ultimately develop highly active and long-term stable steam electrodes for PCECs.ABO3 perovskites with Ba on the A-site and nominally multivalent ions on the B-site are candidates for steam electrodes given the varied compositions in this class that can transport oxide ions, protons, and electronic species, and the lowering of hydration enthalpies by the basicity introduced by Ba. However, very few measurements of k exist for these materials, and the evolution of surface chemistry and thus k is poorly understood.In this work, we fabricated and compared two perovskite triple conducting oxides by growing geometrically well-defined films of Ba(Pr,Y)O3-x (BPY) and Ba(Co,Fe,Zr,Y)O3-x (BCFZY) with pulsed laser deposition. We examined the proton surface exchange coefficients (k-values) using simultaneous in-situ optical transmission relaxation and electrical conductivity relaxation measurements upon switching pH2O at a temperature of 400 ˚C, and continued these switches as a function of time to assess stability. To our knowledge, this is the first use of an optical transmission method to probe elevated temperature steam splitting kinetics, and we interpret the optical (and electrical) changes as indicative of redox during the hydrogenation process. The k-values of BPY thin films were approximately ten times higher than those of the BCFZY thin films, and BPY also retained higher k-values over time. The bulk and surface chemical compositions of BPY and BCFZY thin films before and after relaxation measurements were compared using Rutherford backscattering spectrometry, angle-resolved X-ray photoelectron spectroscopy, and scanning transmission electron microscopy with spectroscopy. Pronounced Ba enrichment and Si contamination (from the quartz tube) were evident at the surface of BPY by both S/TEM-EDS and XPS, whereas for BCFZY these surface chemical features were only detectable by XPS and absent in S/TEM-EDS. Implications for materials design of steam electrodes will be discussed, considering efficiency and lifetime.