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Title: Theoretical exploration of various lithium peroxide crystal structures in a Li-air battery

Journal Article · · Energies
DOI:https://doi.org/10.3390/en8010529· OSTI ID:1201754
 [1];  [2];  [2];  [3];  [1];  [2];  [2]
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Div.
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Div.
  3. Purdue Univ., West Lafayette, IN (United States). School of Chemical Engineering.
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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.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Electrical Energy Storage (CEES)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1201754
Alternate ID(s):
OSTI ID: 1210290; OSTI ID: 1392615
Journal Information:
Energies, Vol. 8, Issue 1; ISSN 1996-1073
Publisher:
MDPI AGCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 13 works
Citation information provided by
Web of Science

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Cited By (3)

Metal-Air Batteries: From Static to Flow System journal August 2018
Ab initio theory of polarons: Formalism and applications journal June 2019
Ab initio theory of polarons: formalism and applications text January 2019

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Related Subjects

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)