Spectroscopic Signature of Oxidized Oxygen States in Peroxides
Abstract
Recent debates on the oxygen redox behaviors in battery electrodes have triggered a pressing demand for the reliable detection and understanding of nondivalent oxygen states beyond conventional absorption spectroscopy. Here, enabled by high-efficiency mapping of resonant inelastic X-ray scattering (mRIXS) coupled with first-principles calculations, we report distinct mRIXS features of the oxygen states in Li2O, Li2CO3, and especially, Li2O2, which are successfully reproduced and interpreted theoretically. mRIXS signals are dominated by valence-band decays in Li2O and Li2CO3. However, the oxidized oxygen in Li2O2 leads to partially unoccupied O-2p states that yield a specific intraband excitonic feature in mRIXS. Such a feature displays a specific emission energy in mRIXS, which disentangles the oxidized oxygen states from the dominating transition-metal/oxygen hybridization features in absorption spectroscopy, thus providing critical hints for both detecting and understanding the oxygen redox reactions in transition-metal oxide based battery materials.
- Authors:
-
[2];
[3];
[4];
[4];
[5];
[4]
- Peking Univ., Shenzhen (People's Republic of China); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Stanford Univ. and SLAC National Accelerator Lab., Menlo Park, CA (United States)
- National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Peking Univ., Shenzhen (People's Republic of China)
- Publication Date:
- Research Org.:
- SLAC National Accelerator Lab., Menlo Park, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1490975
- Alternate Identifier(s):
- OSTI ID: 1563980
- Grant/Contract Number:
- AC02-76SF00515; 2013N080; KYPT20141016105435850; AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry Letters
- Additional Journal Information:
- Journal Volume: 9; Journal Issue: 21; Journal ID: ISSN 1948-7185
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Zhuo, Zengqing, Pemmaraju, Chaitanya Das, Vinson, John, Jia, Chunjing, Moritz, Brian, Lee, Ilkyu, Sallies, Shawn, Li, Qinghao, Wu, Jinpeng, Dai, Kehua, Chuang, Yi-de, Hussain, Zahid, Pan, Feng, Devereaux, Thomas P., and Yang, Wanli. Spectroscopic Signature of Oxidized Oxygen States in Peroxides. United States: N. p., 2018.
Web. doi:10.1021/acs.jpclett.8b02757.
Zhuo, Zengqing, Pemmaraju, Chaitanya Das, Vinson, John, Jia, Chunjing, Moritz, Brian, Lee, Ilkyu, Sallies, Shawn, Li, Qinghao, Wu, Jinpeng, Dai, Kehua, Chuang, Yi-de, Hussain, Zahid, Pan, Feng, Devereaux, Thomas P., & Yang, Wanli. Spectroscopic Signature of Oxidized Oxygen States in Peroxides. United States. https://doi.org/10.1021/acs.jpclett.8b02757
Zhuo, Zengqing, Pemmaraju, Chaitanya Das, Vinson, John, Jia, Chunjing, Moritz, Brian, Lee, Ilkyu, Sallies, Shawn, Li, Qinghao, Wu, Jinpeng, Dai, Kehua, Chuang, Yi-de, Hussain, Zahid, Pan, Feng, Devereaux, Thomas P., and Yang, Wanli. Tue .
"Spectroscopic Signature of Oxidized Oxygen States in Peroxides". United States. https://doi.org/10.1021/acs.jpclett.8b02757. https://www.osti.gov/servlets/purl/1490975.
@article{osti_1490975,
title = {Spectroscopic Signature of Oxidized Oxygen States in Peroxides},
author = {Zhuo, Zengqing and Pemmaraju, Chaitanya Das and Vinson, John and Jia, Chunjing and Moritz, Brian and Lee, Ilkyu and Sallies, Shawn and Li, Qinghao and Wu, Jinpeng and Dai, Kehua and Chuang, Yi-de and Hussain, Zahid and Pan, Feng and Devereaux, Thomas P. and Yang, Wanli},
abstractNote = {Recent debates on the oxygen redox behaviors in battery electrodes have triggered a pressing demand for the reliable detection and understanding of nondivalent oxygen states beyond conventional absorption spectroscopy. Here, enabled by high-efficiency mapping of resonant inelastic X-ray scattering (mRIXS) coupled with first-principles calculations, we report distinct mRIXS features of the oxygen states in Li2O, Li2CO3, and especially, Li2O2, which are successfully reproduced and interpreted theoretically. mRIXS signals are dominated by valence-band decays in Li2O and Li2CO3. However, the oxidized oxygen in Li2O2 leads to partially unoccupied O-2p states that yield a specific intraband excitonic feature in mRIXS. Such a feature displays a specific emission energy in mRIXS, which disentangles the oxidized oxygen states from the dominating transition-metal/oxygen hybridization features in absorption spectroscopy, thus providing critical hints for both detecting and understanding the oxygen redox reactions in transition-metal oxide based battery materials.},
doi = {10.1021/acs.jpclett.8b02757},
journal = {Journal of Physical Chemistry Letters},
number = 21,
volume = 9,
place = {United States},
year = {Tue Oct 16 00:00:00 EDT 2018},
month = {Tue Oct 16 00:00:00 EDT 2018}
}
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Figures / Tables:
Figure 1: (a) Experimental O $K$-edge mRIXS of Li2O, which is dominated by the emission feature around 525 eV emission energy. Color indicates the intensity distribution of the emitted photons, with blue presenting low intensity and white presenting high intensity. (b) Calculated mRIXS of Li2O, which reproduce the dominate featuresmore »
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