Spectroscopic Signature of Oxidized Oxygen States in Peroxides

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

doi:10.1021/acs.jpclett.8b02757

Title: Spectroscopic Signature of Oxidized Oxygen States in Peroxides

Journal Article · 16 October 2018 · Journal of Physical Chemistry Letters

DOI: https://doi.org/10.1021/acs.jpclett.8b02757 · OSTI ID:1490975

Zhuo, Zengqing ^[1];

^[2];

^[3]; Jia, Chunjing ^[2]; Moritz, Brian ^[2]; Lee, Ilkyu ^[2]; Sallies, Shawn ^[4]; Li, Qinghao ^[4]; Wu, Jinpeng ^[4]; Dai, Kehua ^[4];

^[4];

^[5]; Devereaux, Thomas P. ^[2];

^[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)

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.

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Research Organization:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-76SF00515; 2013N080; KYPT20141016105435850; AC02-05CH11231

OSTI ID:: 1490975

Alternate ID(s):: OSTI ID: 1563980

Journal Information:: Journal of Physical Chemistry Letters, Vol. 9, Issue 21; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 74 works

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