Exploring Stable and Selective Anode Materials for the Electrochemical Oxidative Coupling of Methane (EOCM): A Case Study of Doped Titanates
Authors: Grajkowski Filip , Chandra Subhash , Dimitrakopoulos Georgios , Kim Dongha , Yildiz Bilge 
Published: September 2023

The development of next-generation solid oxide fuel cells (SOFCs) relies on integrating materials such as La0.6Sr0.4Co0.2Fe0.8O3-
δ (LSCF), which has been lauded for its fast oxygen ion and electron conduction, along with its high oxygen reduction activity.[1] However, the use of LSCF has been plagued by 1) stability issues caused by surface Sr precipitation and 2) subsequent poisoning by Cr- or S- containing species.
We have previously shown that the introduction of more oxidizable cations at the electrode surface can effectively improve both the stability and the oxygen exchange kinetics of the electrodes. However, the influence of these cations, as with many dopant infiltration studies, is currently not fully understood across all possible modes of electrode surface stabilization/activity enhancement. For example, we have recently discovered that at 800°C and under air atmospheres (i.e. at typical SOFC operational conditions), these Hf/Zr surface cation dopants are mobile and diffuse into the lattice of a porous LSCF electrode as evidenced by their vanishing x-ray photoelectron signals. This is accompanied nevertheless by a noticeable electrode stabilization, suggesting a sub-surface effect of the introduced dopants.
Inspired by this, in this work our aim is to uncover the mechanism responsible for the stabilization of the surface oxygen exchange kinetics. Our approach involves dense thin film LSCF as model system to investigate the temperature-dependent physicochemical properties of these surface and sub-surface dopant cations. We fabricate LSCF thin films via pulsed laser deposition onto single crystalline substrates and then introduce our targeted cations at the surface via an aqueous solution infiltration. We characterize the electrochemical performance of the thin films by performing chronoamperometric and impedance spectroscopic measurements to discern the extent of the temporal electrode performance degradation using metrics such as area-specific resistance. In parallel, we aim to rationalize the observed electrochemical performance stabilization using complementary surface science techniques. We propose investigating the cation dissolution phenomenon through a combination of x-ray photoelectron and Auger electron spectroscopies, along with atomic force microscopy, scanning/transmission electron microscopy, scanning tunnelling microscopy and grazing incidence thin film x-ray diffraction. This study aims to reveal the influence of sub-surface more oxidizable cations on the extent of Sr segregation and highlights how two major factors contribute to the observed trends:

Electrode fabrication conditions, for example the dopant concentration dependence (insufficient or excessive surface dopant concentrations has previously been shown to suppress the stabilization effect).[3]

Electrode operation conditions, for example the temperature profile experienced by the cell (higher temperatures lead to dopant dissolution).

[1] SP Jiang, Int. J. Hydrogen Energy
44 (14), 7448 (2019).
[2] N Tsvetkov et al., Nature Mat.
15 (9), 1010 (2016).
[3] N Tsvetkov et al., Faraday Disc.
182 (0), 257 (2015).