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Title: Spectroscopic Signature of Oxidized Oxygen States in Peroxides

Abstract

Here, 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 Li 2O, Li 2CO 3, and especially, Li 2O 2, which are successfully reproduced and interpreted theoretically. mRIXS signals are dominated by valence-band decays in Li 2O and Li 2CO 3. However, the oxidized oxygen in Li 2O 2 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:
 [1]; ORCiD logo [2]; ORCiD logo [3];  [2];  [2];  [2];  [4];  [4];  [4];  [4]; ORCiD logo [4]; ORCiD logo [4]; ORCiD logo [5];  [2]; ORCiD logo [4]
  1. Peking Univ., Shenzhen (People's Republic of China); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Stanford Univ. and SLAC National Accelerator Lab., Menlo Park, CA (United States)
  3. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  5. Peking Univ., Shenzhen (People's Republic of China)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1490975
Grant/Contract Number:  
AC02-76SF00515; 2013N080; KYPT20141016105435850
Resource Type:
Journal Article: 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. 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., and Yang, Wanli. Tue . "Spectroscopic Signature of Oxidized Oxygen States in Peroxides". United States. doi:10.1021/acs.jpclett.8b02757.
@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 = {Here, 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},
issn = {1948-7185},
number = 21,
volume = 9,
place = {United States},
year = {2018},
month = {10}
}

Journal Article:
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