Pressure-induced phase and chemical transformations of lithium peroxide (Li2O2 )
Abstract
Here, we present the pressure-induced phase/chemical changes of lithium peroxide (Li2O2) to 63 GPa using diamond anvil cells, confocal micro-Raman spectroscopy, and synchrotron x-ray diffraction. The Raman data show the emergence of the major vibrational peaks associated with O2 above 30 GPa, indicating the subsequent pressure-induced reversible chemical decomposition (disassociation) in dense Li2O2. The x-ray diffraction data of Li2O2, on the other hand, show no dramatic structural change but remain well within a P63/mmc structure to 63 GPa. Nevertheless, the Rietveld refinement indicates a subtle change in the structural order parameter z of the oxygen position O (1/3, 2/3, z) at around 35 GPa, which can be considered as a second-order, isostructural phase transition. The nearest oxygen-oxygen distance collapses from 1.56 Å at ambient condition to 1.48 Å at 63 GPa, resulting in a more ionic character of this layered crystal lattice, 3Li++(LiO2)$$3-\atop{3}$$. This structural change in turn advocates that Li2O2 decomposes to 2Li and O2, further augmented by the densification in specific molar volumes.
- Authors:
-
- Washington State Univ., Pullman, WA (United States). Dept. of Chemistry and Inst. for Shock Physics
- Publication Date:
- Research Org.:
- Washington State Univ., Pullman, WA (United States); Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
- Sponsoring Org.:
- USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; USDHS Science and Technology Directorate (S&T) Office of University Programs; Defense Threat Reduction Agency (DTRA); National Science Foundation (NSF)
- Contributing Org.:
- Carnegie Inst. of Washington, Argonne, IL (United States). Geophysical Lab., High Pressure Collaborative Access Team (HPCAT)
- OSTI Identifier:
- 1467875
- Grant/Contract Number:
- NA0001974; 2013-ST-061-ED0001; HDTRA1-12-01-0020; 1203834; FG02-99ER45775
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Chemical Physics
- Additional Journal Information:
- Journal Volume: 145; Journal Issue: 8; Journal ID: ISSN 0021-9606
- Publisher:
- American Institute of Physics (AIP)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; raman spectra; high pressure; rietveld refinement; phase transitions; lattice modes; x-ray diffraction; crystal structure; diamond anvil cells; lithium
Citation Formats
Dunuwille, Mihindra, Kim, Minseob, and Yoo, Choong-Shik. Pressure-induced phase and chemical transformations of lithium peroxide (Li2O2 ). United States: N. p., 2016.
Web. doi:10.1063/1.4961453.
Dunuwille, Mihindra, Kim, Minseob, & Yoo, Choong-Shik. Pressure-induced phase and chemical transformations of lithium peroxide (Li2O2 ). United States. https://doi.org/10.1063/1.4961453
Dunuwille, Mihindra, Kim, Minseob, and Yoo, Choong-Shik. Wed .
"Pressure-induced phase and chemical transformations of lithium peroxide (Li2O2 )". United States. https://doi.org/10.1063/1.4961453. https://www.osti.gov/servlets/purl/1467875.
@article{osti_1467875,
title = {Pressure-induced phase and chemical transformations of lithium peroxide (Li2O2 )},
author = {Dunuwille, Mihindra and Kim, Minseob and Yoo, Choong-Shik},
abstractNote = {Here, we present the pressure-induced phase/chemical changes of lithium peroxide (Li2O2) to 63 GPa using diamond anvil cells, confocal micro-Raman spectroscopy, and synchrotron x-ray diffraction. The Raman data show the emergence of the major vibrational peaks associated with O2 above 30 GPa, indicating the subsequent pressure-induced reversible chemical decomposition (disassociation) in dense Li2O2. The x-ray diffraction data of Li2O2, on the other hand, show no dramatic structural change but remain well within a P63/mmc structure to 63 GPa. Nevertheless, the Rietveld refinement indicates a subtle change in the structural order parameter z of the oxygen position O (1/3, 2/3, z) at around 35 GPa, which can be considered as a second-order, isostructural phase transition. The nearest oxygen-oxygen distance collapses from 1.56 Å at ambient condition to 1.48 Å at 63 GPa, resulting in a more ionic character of this layered crystal lattice, 3Li++(LiO2)$3-\atop{3}$. This structural change in turn advocates that Li2O2 decomposes to 2Li and O2, further augmented by the densification in specific molar volumes.},
doi = {10.1063/1.4961453},
journal = {Journal of Chemical Physics},
number = 8,
volume = 145,
place = {United States},
year = {Wed Aug 24 00:00:00 EDT 2016},
month = {Wed Aug 24 00:00:00 EDT 2016}
}
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