Frequency-Resolved X-Ray Absorption Spectroscopy: A Synchrotron-Based Technique for Extracting Kinetic and Transport Parameters
Authors: Gerwe Brian S , Mizuno Keita , Sekizawa Oki , Nitta Kiyofumi , Amezawa Koji , Adler Stuart B. 
Published: December 2020

Worldwide energy infrastructures are shifting to renewable, but intermittent sources, requiring new solutions for energy storage and conversion. Solid oxide fuel cells are attractive for their high energetic efficiencies, but poor performance in oxygen electrodes contributes to high material costs preventing their widespread adoption. Improving the performance of these technologies is often hindered by inadequate knowledge of localized kinetic and transport behavior. Spatial averaging across the electrode structure makes these properties inaccessible to typical bulk electrochemical characterization techniques like DC polarization and AC impedance spectroscopy. Conversely, chemically sensitive operando and in situ techniques spatially resolve local behavior but struggle to separate physics by timescale. We aim to bridge this gap by extending on previous work using synchrotron-based operando micro X-ray absorption spectroscopy (µ-XAS)1–3 with steady periodic voltage perturbations to isolate and spatiotemporally resolve physics.

We introduce this technique – called frequency-resolved X-ray absorption spectroscopy (fr-XAS)– by showing one-dimensional oxygen vacancy distribution images in a patterned thin film La0.6Sr0.4CoO3-δ electrode. Oxygen vacancies in the electrode are compensated by Co oxidation state, resulting in Co K-edge absorption shifts. At a fixed incident X-ray energy, the edge shifts appear as vertical changes, providing a direct measure of electrode oxidation state in the irradiated volume. Scanning the X-ray beam across the electrode and measuring the absorption shift at each point over time (with Fourier analysis to accurately distinguish shifts caused by the voltage perturbation from noise in the signal) allows us to construct the oxygen vacancy distribution images. The oxygen chemical potential is equilibrated at the electrode/electrolyte interface controlled by the voltage with gradients extending away from the interface determined by surface exchange and ionic transport processes. Changing the perturbation frequency separates observed physics by timescale and allows for directly extracting kinetic and transport parameters.

Initial results show good quantitative agreement with a one-dimensional Gerischer model, and extracted vacancy diffusion coefficients and surface exchange rates are within a factor of 10 from literature values on porous electrodes.4,5 Impedance results from the same sample are obfuscated by extraneous processes past the point of reasonable interpretation, thereby highlighting the power of fr-XAS to extract meaningful parameters despite extraneous factors. These promising results demonstrate proof-of-concept for fr-XAS and provide motivation for the community to adapt this framework for other material systems relevant to energy storage and conversion technologies.

(1) Fujimaki, Y.; Watanabe, H.; Terada, Y.; Nakamura, T.; Yashiro, K.; Hashimoto, S.; Kawada, T.; Amezawa, K. Direct Evaluation of Oxygen Chemical Potential Distribution in an SOFC Cathode by In Situ X-Ray Absorption Spectroscopy. ECS Trans.
2013, 57 (1), 1925–1932. https://doi.org/10.1149/05701.1925ecst.

(2) Amezawa, K.; Fujimaki, Y.; Nakamura, T.; Bagarinao, K. D.-; Yamaji, K.; Nitta, K.; Terada, Y.; Iguchi, F.; Yashiro, K.; Yugami, H.; Kawada, T. (Invited) Determination of Effective Reaction Area in a Mixed-Conducting SOFC Cathode. ECS Trans.
2015, 66 (2), 129–135. https://doi.org/10.1149/06602.0129ecst.

(3) Amezawa, K.; Fujimaki, Y.; Mizuno, K.; Kimura, Y.; Nakamura, T.; Nitta, K.; Terada, Y.; Iguchi, F.; Yugami, H.; Yashiro, K.; Kawada, T. (Invited) Triple Phase Boundary Reaction in a Mixed-Conducting SOFC Cathode. ECS Trans.
2017, 77 (10), 41–47. https://doi.org/10.1149/07710.0041ecst.

(4) Lu, Y.; Kreller, C.; Adler, S. B. Measurement and Modeling of the Impedance Characteristics of Porous La1 − x Sr x CoO3 − δ Electrodes. J. Electrochem. Soc.
2009, 156 (4), B513–B525. https://doi.org/10.1149/1.3079337.

(5) Søgaard, M.; Hendriksen, P. V.; Mogensen, M.; Poulsen, F. W.; Skou, E. Oxygen Nonstoichiometry and Transport Properties of Strontium Substituted Lanthanum Cobaltite. Solid State Ionics
2006, 177 (37), 3285–3296. https://doi.org/10.1016/j.ssi.2006.09.005.