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Energies 2015, 8(1), 529-548; doi:10.3390/en8010529

Theoretical Exploration of Various Lithium Peroxide Crystal Structures in a Li-Air Battery

Materials Science Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, IL 60439, USA
Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, IL 60439, USA
Purdue University, School of Chemical Engineering, Forney Hall of Chemical Engineering, 480 Stadium Mall Drive, West Lafayette, IN 47907-2100, USA
Current Address: Beijing Technology and Business University, Beijing 100048, China
Author to whom correspondence should be addressed.
Academic Editor: Sheng S. Zhang
Received: 11 November 2014 / Accepted: 6 January 2015 / Published: 14 January 2015
(This article belongs to the Special Issue Electrochemical Energy Storage—Battery and Capacitor)
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We describe a series of metastable Li2O2 crystal structures involving different orientations and displacements of the O22− peroxy ions based on the known Li2O2 crystal structure. Within the vicinity of the chemical potential ΔG ~ 0.20 eV/Li from the thermodynamic ground state of the Li2O2 crystal structure (i.e., Föppl structure), all of these newly found metastable Li2O2 crystal structures are found to be insulating and high-k materials, and they have a common unique signature of an O22− O-O vibration mode (ω ~ 799–865 cm−1), which is in the range of that commonly observed in Li-air battery experiments, regardless of the random O22− orientations and the symmetry in the crystal lattice. From XRD patterns analysis, the commercially available Li2O2 powder is confirmed to be the thermodynamic ground state Föppl-like structure. However, for Li2O2 compounds that are grown electrochemically under the environment of Li-O2 cells, we found that the XRD patterns alone are not sufficient for structural identification of these metastable Li2O2 crystalline phases due to the poor crystallinity of the sample. In addition, the commonly known Raman signal of O22− vibration mode is also found to be insufficient to validate the possible existence of these newly predicted Li2O2 crystal structures, as all of them similarly share the similar O22− vibration mode. However considering that the discharge voltage in most Li-O2 cells are typically several tenths of an eV below the thermodynamic equilibrium for the formation of ground state Föppl structure, the formation of these metastable Li2O2 crystal structures appears to be thermodynamically feasible. View Full-Text
Keywords: Li-air battery; lithium peroxide; crystal structure; DFT calculation Li-air battery; lithium peroxide; crystal structure; DFT calculation

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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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MDPI and ACS Style

Lau, K.C.; Qiu, D.; Luo, X.; Greeley, J.; Curtiss, L.A.; Lu, J.; Amine, K. Theoretical Exploration of Various Lithium Peroxide Crystal Structures in a Li-Air Battery. Energies 2015, 8, 529-548.

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