Understanding battery and catalytic reactions via core-level spectroscopies

Materials often undergo local changes in structure and electronic properties during operations. For example, transition metal oxide battery materials and catalysts often undergo coordination and oxidation state changes. In order to probe these changes, core-level spectroscopy including x-ray absorption, emission, non-resonant and resonant inelastic x-ray scattering, as well as electron energy loss spectroscopy, is often informative. Because of the integrated nature of these signals, the interpretation of these experiments can be at times ambiguous, but can be significantly aided by the use of first principles modeling of core-level spectra. In this talk, we discuss the use of OCEAN [1], a code based on the Bethe-Salpeter Equation, for accurate prediction of core-level spectra, and how the results have helped informed oxygen redox accompanying battery reactions [2,3,4] and detection of CO adsorption during catalytic CO2 reduction reaction [5] in transition metal oxides.
1. K. Gilmore, J. Vinson, E.L. Shirley, D. Prendergast, C.D. Pemmaraju, J.J. Kas, F.D. Vila, J.J. Rehr, Comp Phys Comm 197, 109 (2015).
2. C. Zhan, Z. Yao, J. Lu, L. Ma, V. A. Maroni, L. Li, T. Wu, J.G. Wen, Y. Ren, C. Johnson, M. M. Thackeray, M. K. Y. Chan, C. Wolverton, K. Amine, Nature Energy 2, 963 (2017).
3. L. Li, E. J. Lee, J. W. Freeland, T. T. Fister, M. M. Thackeray, M. K. Y. Chan, “Identifying the Chemical Origin of Oxygen Redox Activity in Li-Rich Anti-Fluorite Lithium Iron Oxide by Experimental and Theoretical X-ray Absorption Spectroscopy,” submitted.
4. L. Li, F. C. Castro, J. S. Park, H. Li, E. J. Lee, T. D. Boyko, J. W. Freeland, Z. Yao, T. T. Fister, J. Vinson, E. L. Shirley, C. Wolverton, J. Cabana, V. P. Dravid, M. M. Thackeray, M. K. Y. Chan, “Probing Electrochemically-Induced Structural Evolution and Oxygen Redox Reactions in Li-Rich Layered Cathode Materials,” submitted.
5. L. Li, R. Zhang, R. Zhang, J. Vinson, E. Shirley, J. R. Guest, M. K. Y. Chan, Chem Mater 30, 1912 (2018).