In the Center for Electrochemical Energy Science (CEES) Energy Frontier Research Center, we are investigating a new class of energy storage materials – hybrid Li-ion/Li-oxygen materials – that combine transition metal and oxygen redox chemistries to deliver high energy storage capacity [1, 2, 3]. The electrochemical reactions, structural and electronic structure evolution of these materials are complex, requiring a combination of in-depth characterization and first principles modeling. In this talk, we will report on a comparison study of several examples of hybrid Li-ion/Li-oxygen materials using density functional theory calculations. We will discuss the structural and electronic structure reasons for differences in reaction pathways and competition between transition metal vs oxygen redox chemistries. Insight towards selecting and designing promising hybrid battery materials gleaned from the comparison will be discussed.

[1] L. Trahey, C. S. Johnson, J. T. Vaughey, S.-H. Kang, L. J. Hardwick, S. A. Freunberger, P. G. Bruce, M. M. Thackeray, “Activated Lithium-Metal-Oxides as Catalytic Electrodes for Li-O₂ Cells,” Electrochemical and Solid-State Letters, 2011, 14, A64.

[2] M. M. Thackeray, M. K. Y. Chan, L. Trahey, S. Kirklin, and C. Wolverton, “Vision for Designing High-Energy, Hybrid Li Ion/Li–O₂ Cells,” Journal of Physical Chemistry Letters, 2013, 4, 3607.

[3] Z. Yang, L. Trahey, Y. Ren, M. K. Y. Chan, C. Lin, J. Okasinski, and M. M. Thackeray, “In-Situ High-Energy Synchrotron X-ray Diffraction Studies and First Principles Modeling of α-MnO₂ Electrodes in Li-O₂ and Li-ion Coin Cells,” Journal of Materials Chemistry A, 2015, 3, 7389.