Theoretical exploration of various lithium peroxide crystal structures in a Li-air battery
Abstract
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, asmore »
- Authors:
-
- Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Div.
- Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Div.
- Purdue Univ., West Lafayette, IN (United States). School of Chemical Engineering.
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Electrical Energy Storage (CEES)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1201754
- Alternate Identifier(s):
- OSTI ID: 1210290; OSTI ID: 1392615
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Energies
- Additional Journal Information:
- Journal Volume: 8; Journal Issue: 1; Journal ID: ISSN 1996-1073
- Publisher:
- MDPI AG
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 25 ENERGY STORAGE; Li-air battery; lithium peroxide; crystal structure; DFT calculation; energy storage (including batteries and capacitors); charge transport; materials and chemistry by design; synthesis (novel materials)
Citation Formats
Lau, Kah, Qiu, Dantong, Luo, Xiangyi, Greeley, Jeffrey, Curtiss, Larry, Lu, Jun, and Amine, Khalil. Theoretical exploration of various lithium peroxide crystal structures in a Li-air battery. United States: N. p., 2015.
Web. doi:10.3390/en8010529.
Lau, Kah, Qiu, Dantong, Luo, Xiangyi, Greeley, Jeffrey, Curtiss, Larry, Lu, Jun, & Amine, Khalil. Theoretical exploration of various lithium peroxide crystal structures in a Li-air battery. United States. https://doi.org/10.3390/en8010529
Lau, Kah, Qiu, Dantong, Luo, Xiangyi, Greeley, Jeffrey, Curtiss, Larry, Lu, Jun, and Amine, Khalil. Wed .
"Theoretical exploration of various lithium peroxide crystal structures in a Li-air battery". United States. https://doi.org/10.3390/en8010529. https://www.osti.gov/servlets/purl/1201754.
@article{osti_1201754,
title = {Theoretical exploration of various lithium peroxide crystal structures in a Li-air battery},
author = {Lau, Kah and Qiu, Dantong and Luo, Xiangyi and Greeley, Jeffrey and Curtiss, Larry and Lu, Jun and Amine, Khalil},
abstractNote = {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.},
doi = {10.3390/en8010529},
journal = {Energies},
number = 1,
volume = 8,
place = {United States},
year = {Wed Jan 14 00:00:00 EST 2015},
month = {Wed Jan 14 00:00:00 EST 2015}
}
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