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

Kah Chun Lau, Dantong Qiu, Xiangyi Luo, Jeffrey Greeley, Larry A. Curtiss, Jun Lu and Khalil Amine
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Kah Chun Lau: Materials Science Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, IL 60439, USA
Dantong Qiu: Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, IL 60439, USA
Xiangyi Luo: Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, IL 60439, USA
Jeffrey Greeley: Purdue University, School of Chemical Engineering, Forney Hall of Chemical Engineering, 480 Stadium Mall Drive, West Lafayette, IN 47907-2100, USA
Larry A. Curtiss: Materials Science Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, IL 60439, USA
Jun Lu: Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, IL 60439, USA
Khalil Amine: Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, IL 60439, USA

Energies, 2015, vol. 8, issue 1, 1-20

Abstract: We describe a series of metastable Li 2 O 2 crystal structures involving different orientations and displacements of the O 2 2? peroxy ions based on the known Li 2 O 2 crystal structure. Within the vicinity of the chemical potential ?G ~ 0.20 eV/Li from the thermodynamic ground state of the Li 2 O 2 crystal structure ( i.e. , Föppl structure), all of these newly found metastable Li 2 O 2 crystal structures are found to be insulating and high- k materials, and they have a common unique signature of an O 2 2? O-O vibration mode (? ~ 799–865 cm ?1 ), which is in the range of that commonly observed in Li-air battery experiments, regardless of the random O 2 2? orientations and the symmetry in the crystal lattice. From XRD patterns analysis, the commercially available Li 2 O 2 powder is confirmed to be the thermodynamic ground state Föppl-like structure. However, for Li 2 O 2 compounds that are grown electrochemically under the environment of Li-O 2 cells, we found that the XRD patterns alone are not sufficient for structural identification of these metastable Li 2 O 2 crystalline phases due to the poor crystallinity of the sample. In addition, the commonly known Raman signal of O 2 2? vibration mode is also found to be insufficient to validate the possible existence of these newly predicted Li 2 O 2 crystal structures, as all of them similarly share the similar O 2 2? vibration mode. However considering that the discharge voltage in most Li-O 2 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 Li 2 O 2 crystal structures appears to be thermodynamically feasible.

Keywords: Li-air battery; lithium peroxide; crystal structure; DFT calculation (search for similar items in EconPapers)
JEL-codes: Q Q0 Q4 Q40 Q41 Q42 Q43 Q47 Q48 Q49 (search for similar items in EconPapers)
Date: 2015
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